CN105368350A - Water-dispersible acrylic pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet - Google Patents

Water-dispersible acrylic pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet Download PDF

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Publication number
CN105368350A
CN105368350A CN201510673547.2A CN201510673547A CN105368350A CN 105368350 A CN105368350 A CN 105368350A CN 201510673547 A CN201510673547 A CN 201510673547A CN 105368350 A CN105368350 A CN 105368350A
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alkyl
water
weight
carbonatoms
cation
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CN105368350B (en
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天野立巳
森本有
三井数马
米崎幸介
高岛杏子
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0075—Antistatics
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    • C08L2201/00—Properties
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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    • C09J2433/00—Presence of (meth)acrylic polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

Provided is a water-dispersible acrylic pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer that can prevent static build-up at the time of peeling (antistatic properties), is superior in removability, in the ability to prevent an increase in peel strength (adhesive strength) over time among the adhesive properties, as well as in appearance properties (decrease of appearance defects due to dents or the like), and also in less-staining properties on adherends, particularly, in the ability to prevent white staining on adherends in high-humidity environments (the ability to prevent white staining). The water-dispersible acrylic pressure-sensitive adhesive composition according to the invention contains an acrylic emulsion polymer containing, as monomer components, (i) an alkyl (meth)acrylate, (ii) a carboxyl group-containing unsaturated monomer, and (iii) at least one monomer selected from the group consisting of methyl methacrylate, vinyl acetate, and diethylacrylamide, and an ionic compound, and is characterized in that 70 to 99.5% by weight of the alkyl (meth)acrylate (i) is contained in the total amount of the monomer components.

Description

Water-dispersed acrylic class binder composition, binder layer and adhesive sheet
The divisional application that the application is the applying date is on October 12nd, 2012, application number is the Chinese patent application of 201280051422.0.
Technical field
The present invention relates to the water-dispersed acrylic class binder composition forming the binder layer that can peel off again.Specifically, the present invention relates to that to form bad order, particularly appearance characteristics that static electricity resistance, releasable, adhesion characteristic, minimizing depression etc. cause excellent, and to the low stain of adherend and anti-through time peeling force (bounding force) ascending excellent binder layer water-dispersed acrylic class binder composition.In addition, the present invention relates to the adhesive sheet being provided with the binder layer formed by described binder composition.
The present invention relates to water-dispersed acrylic class binder composition.Specifically, the present invention relates to and form static electricity resistance, adhesion characteristic, water-dispersed acrylic class binder composition to the low stain of adherend and the excellent binder layer of appearance characteristics.In addition, the present invention relates to the binder layer formed by described binder composition, the adhesive sheet being provided with described binder layer and be pasted with the optical component of described adhesive sheet as surface protective film.
Background technology
In the manufacture of the optical component (optical material) being representative with optical thin films such as polarizing plate, polarizer, antireflection plates, manufacturing procedure; for preventing surface scratch, spot, raising cutting processing, suppressing objects such as breaking, the surface of optical component is pasted and uses surface protective film (see patent documentation 1,2).As these surface protective films, the surface being generally used in plastic film substrate is provided with the adhesive sheet of the releasable of the binder layer of releasable.
In the past; use solvent-type acrylic class tackiness agent as tackiness agent (see patent documentation 1,2) in these surface protective film purposes; but; these solvent-type acrylic class tackiness agents contain organic solvent; therefore from the viewpoint of operating environment during coating, water-dispersed acrylic class tackiness agent (see patent documentation 3 ~ 5) is converted to.
These surface protective films require to play sufficient tackiness during pasting on optical component.In addition, be stripped after using in the manufacturing process etc. of optical component, therefore require excellent separability (releasable).In addition, in order to have excellent releasable, except peeling force little (gently peeling off), also need pasting after on the adherends such as optical component, bounding force (peeling force) without time rise characteristic (anti-peeling force (bounding force) is ascending).
In addition, generally speaking, surface protective film or optical component are made up of plastic material, and therefore electrical insulating property is high, produce electrostatic when rubbing or peel off.Therefore, when being peeled off by surface protective film from the optical components such as polarizing plate, producing electrostatic, time under the state that the electrostatic produced at this moment is residual to liquid crystal applied voltages, there is the orientation loss of liquid crystal molecule, and producing the problem of the defect of panel.
In addition, the existence of electrostatic has the possibility of the problem causing the problem, the workability that attract dust or chip to decline etc.Therefore, in order to solve the problem, effects on surface protective film implements various anti-electrostatic process.
As the trial of inhibition zone electrostatic, disclose and add low-molecular-weight tensio-active agent in tackiness agent, tensio-active agent is transferred to from tackiness agent on protected object with the method for anti-electrostatic (such as, see patent documentation 6).But in described method, the low-molecular-weight tensio-active agent of interpolation is easily exuded to adhesive surface, when being applied to surface protective film, worry can pollute adherend (protected object).
In addition; in surface protective film (particularly the surface protective film of optical component) etc.; when there is bad orders such as " depressions " within the adhesive layer, sometimes produce the problems such as the inspection being difficult to carry out adherend under the state being pasted with described surface protective film.Therefore, in the purposes of surface protective film, excellent appearance characteristics is required for adhesive sheet (binder layer).
In addition; in surface protective film purposes (particularly the surface protective film purposes of optical component) etc., the pollution that when adhesive sheet is peeled off, tackiness agent ingredient in residual (so-called " generation of adhesive deposit "), binder layer on adherend (optical component etc.) surface is transferred to first-class adherend surface of causing, adherend surface becomes problems such as the optical characteristics of optical component have a negative impact.Therefore, the low stain to adherend is strongly required for tackiness agent or binder layer.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 11-961 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2001-64607 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2001-131512 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2003-27026 publication
Patent documentation 5: Japanese Patent No. 3810490 specification sheets
Patent documentation 6: Japanese Unexamined Patent Publication 9-165460 publication
Summary of the invention
Invent problem to be solved
But; as mentioned above; in these any one prior aries; all can not balancedly solve the problem; at electrostatic, pollute the relevant technical field of the electronics that becomes the problem of especially severe; present situation is difficult to tackle the requirement improved further the surface protective film with static electricity resistance etc., and not yet obtain the water-dispersed acrylic class tackiness agent with excellent appearance characteristics and releasable.
Therefore, the object of the present invention is to provide can to prevent when can be formed in stripping adherend static electrification (static electricity resistance), releasable, adhesion characteristic and in adhesion characteristic especially anti-through time peeling force (bounding force) ascending excellent and appearance characteristics (reducing the bad order that depression etc. causes) and to the low stain of adherend, the water-dispersed acrylic class binder composition particularly producing the also excellent binder layer of preventive (anti-albefaction contaminative) that albefaction pollutes under high humidity environment on adherend.In addition, the object of the present invention is to provide the adhesive sheet with the binder layer formed by described binder composition and be pasted with the optical component of described adhesive sheet as surface protective film.
For the means of dealing with problems
The present inventor has carried out research extensively and profoundly to achieve these goals, found that, the specific acrylic emulsions type polymkeric substance obtained by starting monomer by specific composition and ionic compound are as constituent, can obtain being formed that static electricity resistance, releasable, adhesion characteristic, anti-peeling force (bounding force) are ascending, the water-dispersed acrylic class binder composition of appearance characteristics and the excellent binder layer of low stain, and complete the present invention.
Namely, water-dispersed acrylic class binder composition of the present invention, it is characterized in that, containing the acrylic emulsions type polymkeric substance formed as monomer component using at least one monomer (iii) in alkyl methacrylate (i), the group that be made up of methyl methacrylate, vinyl-acetic ester and acrylamide containing carboxyl unsaturated monomer (ii) and being selected from and ionic compound, in the total amount of described monomer component, contain the described alkyl methacrylate (i) of 70 ~ 99.5 % by weight.
Water-dispersed acrylic class binder composition of the present invention, preferred described ionic compound is ionic liquid and/or an alkali metal salt.
Water-dispersed acrylic class binder composition of the present invention, preferred described ionic liquid is water-insoluble ionic liquid and/or water soluble ion liquid.
Water-dispersed acrylic class binder composition of the present invention, preferably contains the described monomer (ii) of 0.5 ~ 10 % by weight in the total amount of monomer component.
Water-dispersed acrylic class binder composition of the present invention, preferably contains the described monomer (iii) of 0.5 ~ 10 % by weight in the total amount of monomer component.
Water-dispersed acrylic class binder composition of the present invention, preferred described acrylic emulsions type polymkeric substance uses the reactive emulsifier containing free redical polymerization functional group in molecule to be polymerized.
Water-dispersed acrylic class binder composition of the present invention, preferred described ionic liquid contains at least one positively charged ion in the group being selected from the cation composition represented by following formula (A) ~ (E),
R in formula (A) arepresenting the alkyl of carbonatoms 4 ~ 20, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, R band R cidentical or different, represent the alkyl of hydrogen or carbonatoms 1 ~ 16, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, wherein, when nitrogen-atoms has double bond, there is not R c;
R in formula (B) drepresenting the alkyl of carbonatoms 2 ~ 20, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, R e, R fand R gidentical or different, representing the alkyl of hydrogen or carbonatoms 1 ~ 16, can be the functional group of a part by hybrid atom MCM-41 of described alkyl;
R in formula (C) hrepresenting the alkyl of carbonatoms 2 ~ 20, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, R i, R jand R kidentical or different, representing the alkyl of hydrogen or carbonatoms 1 ~ 16, can be the functional group of a part by hybrid atom MCM-41 of described alkyl;
Z in formula (D) represents nitrogen-atoms, sulphur atom or phosphorus atom, R l, R m, R nand R oidentical or different, represent the alkyl of carbonatoms 1 ~ 20, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, wherein, when Z is sulphur atom, there is not R o;
R in formula (E) prepresenting the alkyl of carbonatoms 1 ~ 18, can be the functional group of a part by hybrid atom MCM-41 of described alkyl.
Water-dispersed acrylic class binder composition of the present invention, the positively charged ion of preferred described ionic liquid is for being selected from by containing imidazoles salt form, containing pyridine salt form, containing morpholine salt form, containing tetramethyleneimine salt form, containing piperidines salt form, ammonium salt-containing type, to contain salt form and at least one contained in the group of sulfonium salt type composition.
Water-dispersed acrylic class binder composition of the present invention, preferred described ionic liquid contains at least one positively charged ion in the group being selected from the cation composition represented by following formula (a) ~ (d),
R in formula (a) 1represent the alkyl of hydrogen or carbonatoms 1 ~ 3, R 2represent the alkyl of hydrogen or carbonatoms 1 ~ 7,
R in formula (b) 3represent the alkyl of hydrogen or carbonatoms 1 ~ 3, R 4represent the alkyl of hydrogen or carbonatoms 1 ~ 7,
R in formula (c) 5represent the alkyl of hydrogen or carbonatoms 1 ~ 3, R 6represent the alkyl of hydrogen or carbonatoms 1 ~ 7,
R in formula (d) 7represent the alkyl of hydrogen or carbonatoms 1 ~ 3, R 8represent the alkyl of hydrogen or carbonatoms 1 ~ 7.
Water-dispersed acrylic class binder composition of the present invention, preferred described an alkali metal salt contains fluo anion.
Water-dispersed acrylic class binder composition of the present invention, preferred described an alkali metal salt is lithium salts.
Water-dispersed acrylic class binder composition of the present invention, preferably containing oxyalkylene copolymerization.
Water-dispersed acrylic class binder composition of the present invention, preferred described oxyalkylene copolymerization also contains the polyether type defoamer that following formula (iv) represents,
HO-(PO) n1，(EO) m1-H(iv)
In formula (iv), PO represents oxygen propylidene, and EO represents oxygen ethylidene, and m1 represents the integer of 0 ~ 40, and n1 represents the integer of more than 1; The addition form of EO and PO is random or block type.
Water-dispersed acrylic class binder composition of the present invention, preferred described oxyalkylene copolymerization is the organopolysiloxane that following formula (vi) represents,
In formula, R 1be the organic group of 1 valency, R 2, R 3and R 4for alkylidene group, R 5for hydrogen or organic group, m and n is the integer of 0 ~ 1000, to be 0, a and b when wherein m, n are different be 0 ~ 100 integer, be 0 when wherein a, b are different.
Water-dispersed acrylic class binder composition of the present invention, preferably also containing have in molecule two or more can with the water-insoluble linking agent of the functional group of carboxyl reaction.
Water-dispersed acrylic class binder composition of the present invention, is preferred for peeling off use again.
Binder layer of the present invention, obtains preferably by by described water-dispersed acrylic class binder composition cross-links.
Binder layer of the present invention, obtains preferably by utilizing described water-insoluble cross-linking agents.
Binder layer of the present invention, the insoluble component content of preferred solvent is more than 90 % by weight, and the elongation at break at 23 DEG C is less than 160%.
Adhesive sheet of the present invention, is preferably formed with aforementioned adhesion oxidant layer at least one side of supporter.
Adhesive sheet of the present invention, preferred described supporter is plastic basis material.
Adhesive sheet of the present invention, is preferred for surface protection.
Adhesive sheet of the present invention, is preferred for optical applications.
Invention effect
The binder layer (adhesive sheet) formed by water-dispersed acrylic class binder composition of the present invention has excellent static electricity resistance, adhesion characteristic (tackiness) and releasable.Particularly, anti-through time and the peeling force (bounding force) of adherend ascending excellent.In addition, low stain, anti-albefaction contaminative when particularly preserving under high humidity environment are excellent.In addition, water-dispersed acrylic class binder composition of the present invention uses the acrylic emulsions type polymkeric substance of specific monomer composition, therefore the binder composition obtained can form the bad order reducing depression etc. and cause, and has the binder layer of very excellent appearance characteristics.Therefore, water-dispersed acrylic class binder composition of the present invention is particularly useful as the surface protection purposes of optical thin film.
Accompanying drawing explanation
Fig. 1 is the sketch chart in potential measurement portion.
Embodiment
The feature of water-dispersed acrylic class binder composition (being sometimes referred to as " binder composition ") of the present invention is, containing the acrylic emulsions type polymkeric substance formed as monomer component using at least one monomer (iii) in alkyl methacrylate (i), the group that be made up of methyl methacrylate, vinyl-acetic ester and acrylamide containing carboxyl unsaturated monomer (ii) and being selected from and ionic compound, in the total amount of described monomer component, contain the described alkyl methacrylate (i) of 70 ~ 99.5 % by weight.In addition, " aqueous dispersion type " refers to and can be distributed in aqueous medium, namely refers to the binder composition that can be distributed in aqueous medium.Described aqueous medium is the medium (dispersion medium) using water as neccessary composition, except independent water, can also be the mixture of water and water-miscible organic solvent.In addition, binder composition of the present invention can for using the dispersion liquid of described aqueous medium etc.
[acrylic emulsions type polymkeric substance]
The acrylic emulsions type polymkeric substance of acrylic emulsions type polymkeric substance of the present invention for being formed using at least one monomer (iii) in alkyl methacrylate (i), the group that is made up of methyl methacrylate, vinyl-acetic ester and acrylamide containing carboxyl unsaturated monomer (ii) and being selected from as monomer component.In addition, in the present invention, (methyl) vinylformic acid refers to vinylformic acid and/or methacrylic acid.
Aforementioned alkyl methacrylate (i) uses as main monomer component, mainly plays a part to show the fundamental characteristics as tackiness agent (or binder layer) such as tackiness, separability.Wherein, it is soft that alkyl acrylate has the polymer flexible giving formation binder layer, play the tendency making binder layer show adhesivity, fusible effect, alkyl methacrylate has the polymkeric substance hardness of giving and forming binder layer, plays the tendency of the effect of the releasable regulating binder layer.As aforementioned (methyl) alkyl acrylate (i), be not particularly limited, (methyl) alkyl acrylate etc. of straight chain, side chain or the cyclic alkyl with carbonatoms 2 ~ 16 (more preferably 2 ~ 10, further preferably 4 ~ 8) can be enumerated.In addition, methyl methacrylate is not comprised in aforementioned (methyl) alkyl acrylate (i).
Wherein, as alkyl acrylate, preference, as having the alkyl acrylate of the alkyl of carbonatoms 2 ~ 14 (more preferably 4 ~ 9), can enumerate the alkyl acrylate etc. that n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, isoamyl acrylate, Ethyl acrylate, heptylacrylate, Octyl acrylate, 2-EHA, Isooctyl acrylate monomer, vinylformic acid ester in the ninth of the ten Heavenly Stems, vinylformic acid ester in the different ninth of the ten Heavenly Stems etc. have straight or branched alkyl.Wherein preferred 2-EHA.
In addition, as alkyl methacrylate, preference, as having the alkyl methacrylate of the alkyl of carbonatoms 2 ~ 16 (more preferably 2 ~ 10), can enumerate β-dimethyl-aminoethylmethacrylate, the ester ring type alkyl methacrylate etc. such as alkyl methacrylate that propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid secondary butyl ester, Tert-butyl Methacrylate etc. have straight or branched alkyl or cyclohexyl methacrylate, methacrylic acid norbornene ester, isobornyl methacrylate.
Described (methyl) alkyl acrylate (i) suitably can be selected according to target binding property etc., may be used singly or two or more in combination.
The content of described (methyl) alkyl acrylate (i) is not particularly limited, in the total amount (total amount of monomer component: be 70 ~ 99.5 % by weight 100 % by weight) of the monomer component of the raw material as formation acrylic emulsions type polymkeric substance of the present invention, preferably 70 ~ 99 % by weight, more preferably 85 ~ 98 % by weight, further preferably 87 ~ 96 % by weight.By described content is set as more than 70 % by weight, tackiness, the releasable of binder layer improve, therefore preferably.On the other hand, when content is more than 99.5 % by weight, the content containing carboxyl unsaturated monomer (ii), monomer (iii) declines, thus, and the degraded appearance of the binder layer sometimes formed by binder composition.In addition, when using two or more (methyl) alkyl acrylates (i), as long as the total amount (total amount) of whole (methyl) alkyl acrylates (i) meets described scope.
The described carboxyl unsaturated monomer (ii) that contains can form protective layer on the emulsion particle surface that comprise acrylic emulsions type polymkeric substance of the present invention, plays the function preventing the shear fracture of particle.This effect is by improving further with carboxyl with in alkali.In addition, the stability of particle to shear fracture more generally refers to mechanical stability.In addition, by combinationally using linking agent (in the present invention, preferred water-insoluble linking agent) that is a kind of or two or more and carboxyl reaction, also can work as cross-linking set in the stage by forming binder layer except anhydrating.In addition, can also be improved and the adhesivity of base material (anchoring) by linking agent (water-insoluble linking agent).Contain carboxyl unsaturated monomer (ii) as such, can enumerate such as: (methyl) vinylformic acid (vinylformic acid, methacrylic acid), methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, carboxyethyl acrylates, vinylformic acid carboxyl pentyl ester etc.In addition, containing also comprising maleic anhydride, itaconic anhydride etc. in carboxyl unsaturated monomer (ii) containing anhydride group unsaturated monomer.In the middle of these, high from the viewpoint of the relative concentration at particle surface, be easy to form more highdensity protective layer, preferred vinylformic acid.
The described content containing carboxyl unsaturated monomer (ii) is not particularly limited, in the total amount (total amount of monomer component: be preferably 0.5 ~ 10 % by weight 100 % by weight) of the starting monomer of formation acrylic emulsions type polymkeric substance of the present invention, more preferably 1 ~ 6 % by weight, further preferably 1 ~ 5 % by weight, particularly preferably 2 ~ 5 % by weight, most preferably 2 ~ 4 % by weight.By described content is set as less than 10 % by weight; can suppress to increase with the interaction of the functional group on the surface of the polarizing plate as adherend (protected object) etc. after formation binder layer; suppress through time peeling force (bounding force) increase; improve separability, therefore preferably.In addition, when content is more than 10 % by weight, be generally water miscible containing carboxyl unsaturated monomer (ii) (such as, vinylformic acid), be therefore sometimes polymerized in water and cause thickening (viscosity increase).In addition, when there is a large amount of carboxyl in the skeleton of described acrylic emulsions type polymkeric substance, infer that the ionic compound (ionic liquid or an alkali metal salt etc.) coordinated with as antistatic agent interacts, hinder ionic conduction, can not get the antistatic performance to adherend, therefore not preferred.On the other hand, by described content is set as more than 0.5 % by weight, the mechanical stability of emulsion particle improves, therefore preferably.In addition, the adhesivity (anchoring) of binder layer and supporter (base material) improves, and can suppress generation of adhesive deposit, therefore preferably.
Aforementioned monomer (iii) (being selected from least one in the group be made up of methyl methacrylate, vinyl-acetic ester and acrylamide) mainly plays the effect reducing macroscopic irregularity.These monomers (iii) in polymerization with other monomer polymerization, its polymer formation emulsion particle, increases the stability of emulsion particle thus, reduce jello (condensation product).In addition, when using water-insoluble linking agent as linking agent, increase with the affinity of hydrophobic water-insoluble linking agent, the dispersiveness of emulsion particle can be improved, reduce by the depression of the bad binder layer caused of dispersion.In addition, increase with the affinity of water-insoluble (hydrophobicity) ionic liquid, producing the inhibition raising of polluting owing to disperseing bad when the addition of described ionic liquid is many, is optimal way.
The content of described monomer (iii) is not particularly limited, in the total amount (total amount of monomer component: be preferably 0.5 ~ 10 % by weight 100 % by weight) of the starting monomer of formation acrylic emulsions type polymkeric substance of the present invention, more preferably 1 ~ 6 % by weight, further preferably 2 ~ 5 % by weight.By aforementioned content is set as less than 10 % by weight, the polymkeric substance forming binder layer is soft, improves with the adhesivity of adherend.In addition, the macroscopic irregularity of binder layer can be suppressed, therefore preferably.On the other hand, by described content is set as more than 0.5 % by weight, the mechanical stability of emulsion particle improves, therefore preferably.In addition, the effect (inhibition of bad order) coordinating monomer (iii) can fully be obtained, therefore preferably.In addition, form in the total amount of the monomer component of acrylic emulsions type polymkeric substance of the present invention, during containing the two or more monomer be selected from the group that is made up of methyl methacrylate, vinyl-acetic ester and acrylamide, the total (total content) of the content of methyl methacrylate, vinyl-acetic ester and acrylamide is aforementioned " content of monomer (iii) ".
As the starting monomer forming acrylic emulsions type polymkeric substance of the present invention, in order to give specific function, also can be used together other monomer component beyond aforementioned neccessary composition [alkyl methacrylate (i), containing carboxyl unsaturated monomer (ii), monomer (iii)].As such monomer component, such as, in order to crosslinked in emulsion particle and raising cohesive force, (use) (methyl) glycidyl acrylate etc. can be added with the ratio being less than 5 % by weight separately and contain epoxy based monomers, polyfunctional monomer such as trimethylolpropane tris (methyl) acrylate, Vinylstyrene etc.In addition, described addition (usage quantity) is the total amount (total amount of monomer component: the content 100 % by weight) at the starting monomer forming acrylic emulsions type polymkeric substance of the present invention.
As other monomer component described, pollute from the viewpoint of reducing albefaction further, the addition (usage quantity) of the hydroxyl unsaturated monomers such as preferred vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester is few.Specifically, (total amount (total amount of monomer component: the content 100 % by weight)) forming the starting monomer of acrylic emulsions type polymkeric substance of the present invention is preferably less than 1 % by weight to the addition of hydroxyl unsaturated monomer, be more preferably less than 0.1 % by weight, further preferably in fact not containing (such as, being less than 0.05 % by weight).But, when in order to introduce crosslinked etc. the cross-linking set of the crosslinked of hydroxyl and isocyanate group or metal corsslinking, also can add (use) about 0.01 ~ about 10 % by weight.
In addition, (monomer mixture) letex polymerization of described starting monomer can obtain by utilizing emulsifying agent, polymerization starter by acrylic emulsions type polymkeric substance of the present invention.
As the emulsifying agent used in aforementioned letex polymerization, preferably use the reactive emulsifier (reactive emulsifier containing free redical polymerization functional group) introducing free redical polymerization functional group in molecule.These emulsifying agents can be used alone or use two or more.
[reactive emulsifier]
The described reactive emulsifier (hereinafter referred to as " reactive emulsifier ") containing free redical polymerization functional group is (in a part) emulsifying agent containing at least one free redical polymerization functional group in molecule.As described reactive emulsifier, be not particularly limited, can from choice for use the various reactive emulsifiers with free redical polymerization functional groups such as vinyl, propenyl, pseudoallyl, vinyl ether (vinyloxy group), allyl ethers (allyloxy) one or more.By using described reactive emulsifier, emulsifying agent is brought in polymkeric substance, and the pollution deriving from emulsifying agent reduces, therefore preferably.
As described reactive emulsifier, can enumerate such as: there is the reactive emulsifier introducing the form (or being equivalent to described form) of the free redical polymerization functional group (free-radical reactive group) such as propenyl or allyl ether in the non-ionic anion type emulsifying agents (having the anionic emulsifier of the hydrophilic radical of nonionic) such as polyethylene oxide alkyl ethers sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether sodium sulfate, polyethylene oxide alkyl ethers sodium sulfosuccinate.In addition, below the reactive emulsifier with the form introducing free redical polymerization functional group in anionic emulsifier is called " anionic reactive emulsifier ".In addition, be called having the reactive emulsifier introducing the form of free redical polymerization functional group in non-ionic anion type emulsifying agent " non-ionic anion type reactive emulsifier ".
Particularly, when using anionic reactive emulsifier (wherein especially non-ionic anion type reactive emulsifier), emulsifying agent is brought in polymkeric substance, can improve low stain thus.In addition, when particularly water-insoluble linking agent of the present invention is multi-functional epoxy's class linking agent with epoxy group(ing), the reactivity of linking agent can be improved by its katalysis.When not using anionic reactive emulsifier, do not stop in aging middle crosslinking reaction, sometimes produce through time binder layer the problem that changes of peeling force (bounding force).In addition, described anionic reactive emulsifier is brought in polymkeric substance, therefore can not as the quaternary ammonium compound that uses as the catalyzer of epoxies linking agent (such as, see Japanese Unexamined Patent Publication 2007-31585 publication) separate out on the surface of adherend like that, therefore albefaction can not be caused to pollute, therefore preferably.
As such reactive emulsifier, also can the commercially available product such as commodity in use name " ア デ カ リ ア ソ ー プ SE-10N " (Asahi Denka Co., Ltd.'s manufacture), trade(brand)name " ア Network ア ロ Application HS-10 " (Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture), trade(brand)name " ア Network ア ロ Application HS-05 " (Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture), trade(brand)name " ア Network ア ロ Application HS-1025 " (Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture).
In addition, particularly foreign ion becomes problem sometimes, therefore preferably removes foreign ion, uses SO 4 2-ionic concn is the emulsifying agent of 100 below μ g/g.In addition, when anionic emulsifier, preferably use ammonium salt emulsifying agent.As the method removing impurity from emulsifying agent, the appropriate means such as contamination precipitation filtration method of ion-exchange-resin process, membrane separation process, use alcohol can be used.
The use level (usage quantity) of described reactive emulsifier is preferably 0.1 ~ 10 weight part relative to total amount (total amount of monomer component) 100 weight parts of the starting monomer forming acrylic emulsions type polymkeric substance of the present invention, more preferably 0.5 ~ 8 weight part, preferred 1 ~ 7 weight part further, further preferred 1 ~ 6 weight part, particularly preferably 1 ~ 5 weight part, particularly preferably 1 ~ 4.5 weight part, most preferably 2 ~ 4.5 weight parts.By use level is set as more than 0.1 weight part, stable emulsification can be kept, therefore preferably.On the other hand, by use level is set as below 10 weight parts, easily the insoluble component content of solvent of the acrylic adhesives film after crosslinked is controlled in the scope specified in the present invention, the cohesive force of tackiness agent (binder layer) can be improved, suppress the pollution to adherend, and the pollution that emulsifying agent causes can be suppressed, therefore preferably.
As the polymerization starter used in aforementioned letex polymerization, be not particularly limited, can use such as: 2,2 '-Diisopropyl azodicarboxylate, 2, two (2-amidine propane) dihydrochloride, 2 of 2 '-azo, two [2-(5-methyl-2-tetrahydroglyoxaline-2-base) propane] dihydrochloride, 2 of 2 '-azo, two (the 2-methyl-prop amidine) dithionate, 2 of 2 '-azo, the azo type polymerization initiators such as 2 '-azo two (N, N '-dimethyleneisobutylamidine); The persulphate such as Potassium Persulphate, ammonium persulphate; The peroxide type polymerization initiators such as benzoyl peroxide, tertbutyl peroxide, hydrogen peroxide; The redox type initiator that superoxide and reductive agent combine, the oxidation-reduction type polymerization starter etc. that the combination (combination etc. of aqueous hydrogen peroxide solution and iron (II) salt) of the combination (combination etc. of aqueous hydrogen peroxide solution and xitix) of such as superoxide and xitix, superoxide and iron (II) salt, persulphate and sodium bisulfite combine.
The use level (usage quantity) of described polymerization starter suitably can be determined according to the kind etc. of initiator or starting monomer, be not particularly limited, consider from the viewpoint such as the insoluble component content of solvent of the acrylic adhesives film after crosslinked being controlled in preferable range, be preferably 0.01 ~ 1 weight part relative to total amount (total amount of monomer component) 100 weight parts of the starting monomer forming acrylic emulsions type polymkeric substance of the present invention, be more preferably 0.02 ~ 0.5 weight part.
Monomer component can be carried out emulsion polymerization to carry out by utilizing ordinary method by aforementioned letex polymerization in water after emulsification.Thus, the aqueous dispersions (polymer emulsion) containing polymkeric substance based on described acrylic emulsions type polymkeric substance can be prepared.As the method for emulsion polymerization, be not particularly limited, can adopt such as: the known emulsion polymerization methods such as fed batch method (batchwise polymerization method), monomer dripping method, monomer emulsion dripping method.In addition, in monomer dripping method, monomer emulsion dripping method, can suitably select to drip continuously or segmentation dropping.These methods can be appropriately combined.Reaction conditionss etc. can suitably be selected, and polymerization temperature is such as preferably about 40 DEG C ~ about 95 DEG C, and polymerization time is preferably about 30 minutes ~ about 24 hours.
The insoluble component content of the solvent (ratio of the insoluble composition of solvent of acrylic emulsions type polymkeric substance of the present invention, sometimes also referred to as " gel fraction "), from the viewpoint of low stain and suitable peeling force (bounding force), be more than 70% (% by weight), preferably more than 75 % by weight, more preferably more than 80 % by weight.The insoluble component content of solvent lower than 70 % by weight time, containing a large amount of low molecular weight substance in acrylic emulsions type polymkeric substance, therefore the low molecular weight compositions in binder layer can not be reduced fully only by crosslinked effect, therefore sometimes produce the adherend deriving from low molecular weight compositions etc. to pollute, or peeling force (bounding force) is too high.The insoluble component content of described solvent can pass through the controls such as the kind of polymerization starter, temperature of reaction, emulsifying agent or starting monomer.The higher limit of the insoluble component content of described solvent is not particularly limited, such as, be 99 % by weight.In addition, in the present invention, the value that the insoluble component content of solvent of acrylic emulsions type polymkeric substance is calculated by following " measuring method of the insoluble component content of solvent ".
[measuring method of the insoluble component content of solvent]
Get about 0.1g acrylic emulsions type polymkeric substance, with porous tetrafluoroethylene sheet (trade(brand)name " NTF1122 ", the Nitto Denko Corp manufactures) parcel of mean pore size 0.2 μm, then tighten with kite string, measure weight now, using described weight as the front weight of dipping.In addition, before described dipping, weight is the gross weight of acrylic emulsions type polymkeric substance (above-mentioned got polymkeric substance), tetrafluoroethylene sheet and kite string.In addition, the total weight of tetrafluoroethylene sheet and kite string is measured, using described weight as packing bag weight.Then, by above-mentioned acrylic emulsions type polymkeric substance tetrafluoroethylene sheet parcel and the object tightened with kite string and obtain (being called " sample ") puts into the 50ml container being full of ethyl acetate, and 23 DEG C leave standstill 7 days.Then, take out sample (after ethyl acetate process) from container, transfer in aluminum cup, 130 DEG C in drying machine dry 2 hours and after removing ethyl acetate, gravimetry, using described weight as weight after dipping.Further, the insoluble component content of solvent is calculated by following formula.In addition, a is weight after dipping, and b is packing bag weight, and c is weight before dipping.
The insoluble component content of solvent (% by weight)=(a-b)/(c-b) × 100
The weight-average molecular weight (Mw) of the solvent-soluble composition (being sometimes referred to as " colloidal sol composition ") of acrylic emulsions type polymkeric substance of the present invention is preferably 40,000 ~ 200,000, and more preferably 50,000 ~ 150,000, further preferably 60,000 ~ 100,000.Be more than 40,000 by the weight-average molecular weight of the solvent-soluble composition of acrylic emulsions type polymkeric substance, binder composition improves the wettability of adherend, improves the tackiness of adherend.In addition, be less than 200,000 by the weight-average molecular weight of the solvent-soluble composition of acrylic emulsions type polymkeric substance, the residual quantity of binder composition on adherend reduces, and improves the low stain of adherend.The weight-average molecular weight of the solvent-soluble composition of described acrylic emulsions type polymkeric substance, can measure air-dry at normal temperatures for the treatment solution (ethyl acetate solution) after the ethyl acetate process that obtains in the mensuration of the insoluble component content of solvent of aforesaid acrylic emulsions type polymkeric substance and sample (the solvent-soluble composition of acrylic emulsions type polymkeric substance) that is that obtain is obtained by utilizing GPC (gel permeation chromatography).Concrete measuring method can enumerate following method.
[measuring method of weight-average molecular weight (Mw)]
GPC measures the GPC device " HLC-8220GPC " using TOSOH Co., Ltd to manufacture to carry out, and obtains molecular weight by polystyrene conversion value.Condition determination is as follows.
Sample concentration: 0.2 % by weight (THF solution)
Sample injection amount: 10 μ l
Elutriant: THF
Flow velocity: 0.6ml/ minute
Measure temperature: 40 DEG C
Post:
Sample column: TSKguardcolumnSuperHZ-H+TSKgelSuperHZM-H two
Reference column: TSKgelSuperH-RC mono-
Detector: differential refractometer
[ionic compound]
Ionic compound in the present invention is not particularly limited, and can enumerate such as ionic liquid, an alkali metal salt, as foregoing ion liquid, can enumerate water-insoluble ionic liquid and water soluble ion liquid.By using foregoing ion compound, excellent antistatic performance can be given.
[water-soluble (wetting ability) ionic liquid]
Water-soluble (wetting ability) ionic liquid in the present invention refers to the melting salt (ionic compound) be in a liquid state at 25 DEG C, be not particularly limited, for the reason obtaining excellent anti-static ability, preferably use the ionic liquid comprising organic cation composition that following formula (A) ~ (E) represents and anionic component.In addition, when water-soluble (wetting ability) ionic liquid is used together with water-insoluble (hydrophobicity) linking agent, compared with using the situation of water-insoluble (hydrophobicity) ionic liquid, can suppress macroscopic irregularity, be therefore useful.In addition, sometimes by water-soluble (wetting ability) ionic liquid referred to as ionic liquid (ionic liquid).
R in above formula (A) arepresent the alkyl of carbonatoms 4 ~ 20, a part for described alkyl can by hybrid atom MCM-41, R band R cidentical or different, representing the alkyl of hydrogen or carbonatoms 1 ~ 16, by hybrid atom MCM-41, wherein, when nitrogen-atoms has double bond, can there is not R in a part for described alkyl c.
R in above formula (B) drepresent the alkyl of carbonatoms 2 ~ 20, a part for described alkyl can by hybrid atom MCM-41, R e, R fand R gidentical or different, represent the alkyl of hydrogen or carbonatoms 1 ~ 16, a part for described alkyl can by hybrid atom MCM-41.
R in above formula (C) hrepresent the alkyl of carbonatoms 2 ~ 20, a part for described alkyl can by the functional group of hybrid atom MCM-41, R i, R jand R kidentical or different, represent the alkyl of hydrogen or carbonatoms 1 ~ 16, a part for described alkyl can by hybrid atom MCM-41.
Z in above formula (D) represents nitrogen-atoms, sulphur atom or phosphorus atom, R l, R m, R nand R oidentical or different, representing the alkyl of carbonatoms 1 ~ 20, by hybrid atom MCM-41, wherein, when Z is sulphur atom, can there is not R in a part for described alkyl o.
R in above formula (E) prepresenting the alkyl of carbonatoms 1 ~ 18, can be the functional group of a part by hybrid atom MCM-41 of described alkyl.
As the positively charged ion that formula (A) represents, can enumerate such as: pyridine positively charged ion, piperidines positively charged ion, tetramethyleneimine positively charged ion, the positively charged ion with pyrroline skeleton, the positively charged ion with pyrrole skeleton, morpholine positively charged ion etc.
As concrete example, for example can enumerate: 1-ethylpyridine Cation, 1-butyl-pyridinium Cation, 1-hexyl pyridine Cation, 1-butyl-3-picoline Cation, 1-butyl-4-picoline Cation, 1-hexyl-3-picoline Cation,1-butyl-3,4-lutidines Cation, 1-ethyl-3-hydroxymethylpyridine Cation, 1,1-dimethyl pyrrolidine Cation, 1-ethyl-1-crassitude Cation, 1-methyl isophthalic acid-propyl pyrrole alkane Cation, 1-methyl isophthalic acid-butyl pyrrolidine Cation,1-methyl-1-pentene base pyrrolidines Cation, 1-methyl isophthalic acid-hexyl pyrrolidines Cation, 1-methyl isophthalic acid-heptyl pyrrolidines Cation, 1-ethyl-1-propyl pyrrole alkane Cation, 1-ethyl-1-butyl pyrrolidine Cation, 1-ethyl-1-amyl group pyrrolidines Cation,1-ethyl-1-hexyl pyrrolidines Cation, 1-ethyl-1-heptyl pyrrolidines Cation, 1,1-dipropyl pyrrolidines Cation, 1-propyl group-1-butyl pyrrolidine Cation, 1,1-dibutyl pyrrolidines Cation, 1-propylpiperdine Cation,1-amyl piperidine Cation, 1,1-lupetidine Cation, 1-methyl isophthalic acid-ethyl piperidine Cation, 1-methyl isophthalic acid-propylpiperdine Cation, 1-methyl isophthalic acid-butyl piperidine Cation, 1-methyl-1-pentene phenylpiperidines Cation,1-methyl isophthalic acid-hexyl piperidines Cation, 1-methyl isophthalic acid-heptyl piperidines Cation, 1-ethyl-1-propylpiperdine Cation, 1-ethyl-1-butyl piperidine Cation, 1-ethyl-1-amyl piperidine Cation, 1-ethyl-1-hexyl piperidines Cation,1-ethyl-1-heptyl piperidines Cation, 1,1-dipropyl piperidines Cation, 1-propyl group-1-butyl piperidine Cation, 1,1-dibutyl piperidines Cation, 2-methyl isophthalic acid-pyrrolin cation, 1-ethyl-2-phenylindone cation, 1,2-dimethyl indole cation, 1-ethyl carbazole cation, N-ethyl-N-methylmorpholinium Cation.
As the positively charged ion that formula (B) represents, can enumerate such as: imidazoles positively charged ion, tetrahydropyrimidine positively charged ion, dihydro-pyrimidin positively charged ion etc.
As concrete example, can enumerate such as: 1,3-methylimidazole positively charged ion, 1,3-diethyl imidazolium positively charged ion, 1-ethyl-3-methylimidazole positively charged ion, 1-butyl-3-Methylimidazole positively charged ion, 1-hexyl-3-Methylimidazole positively charged ion, 1-octyl group-3-Methylimidazole positively charged ion, 1-decyl-3-Methylimidazole positively charged ion, 1-dodecyl-3-Methylimidazole positively charged ion, 1-tetradecyl-3-Methylimidazole positively charged ion, 1,2-dimethyl-3-propyl imidazole positively charged ion, 1-ethyl-2,3-methylimidazole positively charged ion, 1-butyl-2,3-methylimidazole positively charged ion, 1-hexyl-2,3-methylimidazole positively charged ion, 1-(2-hydroxyethyl)-3-Methylimidazole positively charged ion, 1-allyl group-3-Methylimidazole positively charged ion, 1,3-dimethyl-1,4,5,6-tetrahydrochysene pyrimidine positively charged ion, 1,2,3-trimethylammonium-Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine positively charged ion, 1,2,3,4-tetramethyl--Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine positively charged ion, 1,2,3,5-tetramethyl--Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine positively charged ion, 1,3-dimethyl-Isosorbide-5-Nitrae-dihydro-pyrimidin positively charged ion, 1,3-dimethyl-1,6-dihydro-pyrimidin positively charged ion, 1,2,3-trimethylammonium-Isosorbide-5-Nitrae-dihydro-pyrimidin positively charged ion, 1,2,3-trimethylammonium-1,6-dihydro-pyrimidin positively charged ion, 1,2,3,4-tetramethyl--Isosorbide-5-Nitrae-dihydro-pyrimidin positively charged ion, 1,2,3,4-tetramethyl--1,6-dihydro-pyrimidin positively charged ion etc.
As the positively charged ion that formula (C) represents, can enumerate such as: pyrazoles positively charged ion, pyrazoline positively charged ion etc.
As concrete example, can enumerate such as: 1-methylpyrazole positively charged ion, 3-methylpyrazole positively charged ion, 1-Ethyl-2-Methyl pyrazoles positively charged ion, 1-ethyl-2,3,5-trimethylpyrazol positively charged ion, 1-propyl group-2,3,5-trimethylpyrazol positively charged ion, 1-butyl-2,3,5-trimethylpyrazol positively charged ion, 1-ethyl-2,3,5-trimethylpyrazol quinoline positively charged ion, 1-propyl group-2,3,5-trimethylpyrazol quinoline positively charged ion, 1-butyl-2,3,5-trimethylpyrazol quinoline positively charged ion etc.
As the positively charged ion that formula (D) represents, can enumerate such as: tetraalkylammonium cation, trialkylsulfonium cation, tetraalkyl the positively charged ion etc. that the part of positively charged ion, described alkyl is replaced by thiazolinyl, alkoxyl group, hydroxyl, cyano group and epoxy group(ing).
As concrete example, can enumerate such as: tetramethylammonium cation, tetraethylammonium cation, tetrabutyl ammonium cation, four pentyl ammonium cation, tetrahexyl ammonium positively charged ion, four heptyl ammonium cations, triethyl methyl ammonium cation, tributyl ethyl ammonium cations, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium cation, glycidyltrimetiiylammonium ammonium cation, trimethylsulfonium positively charged ion, triethyl sulfonium cation, tributyl sulfonium cation, three hexyl sulfonium cations, diethylmethyl sulfonium cation, dibutylethyl sulfonium cation, tetramethyl- positively charged ion, tetraethyl- positively charged ion, the tetrabutyl positively charged ion, four hexyls positively charged ion, four octyl groups positively charged ion, triethyl methyl positively charged ion, tributyl ethyl positively charged ion, diallyl dimethyl ammonium positively charged ion, choline cation etc.Wherein, preferably triethyl methyl ammonium cation, tributyl ethyl ammonium cations, diethylmethyl sulfonium cation, dibutylethyl sulfonium cation, triethyl methyl is used positively charged ion, tributyl ethyl positively charged ion, trimethyldecylammonium the asymmetrical tetraalkylammonium cation such as positively charged ion, trialkylsulfonium cation, tetraalkyl positively charged ion, or N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium cation, glycidyltrimetiiylammonium ammonium cation, diallyl dimethyl ammonium positively charged ion, N, N-dimethyl-N-ethyl-N-propyl ammonium positively charged ion, N, N-dimethyl-N-ethyl-N-butyl ammonium cation, N, N-dimethyl-N-ethyl-N-amyl group ammonium cation, N, N-dimethyl-N-ethyl-N-hexyl ammonium cation, N, N-dimethyl-N-ethyl-N-heptyl ammonium cation, N, N-dimethyl-N-ethyl-N-nonyl ammonium cation, N, N-dimethyl-N, N-dipropylammonium positively charged ion, N, N-diethyl-N-propyl-N-butyl ammonium cation, N, N-dimethyl-N-propyl group-N-amyl group ammonium cation, N, N-dimethyl-N-propyl group-N-hexyl ammonium cation, N, N-dimethyl-N-propyl group-N-heptyl ammonium cation, N, N-dimethyl-N-butyl-N-hexyl ammonium cation, N, N-diethyl-N-butyl-N-heptyl ammonium cation, N, N-dimethyl-N-amyl group-N-hexyl ammonium cation, N, N-dimethyl-N, N-dihexyl ammonium cation, trimethylammonium heptyl ammonium cation, N, N-diethyl-N-Methyl-N-propyl ammonium cation, N, N-diethyl-N-methyl--V-pentyl ammonium cation, N, N-diethyl-N-methyl-N-heptyl ammonium cation, N, N-diethyl-N-propyl-N-amyl group ammonium cation, triethyl propyl ammonium positively charged ion, triethyl amyl group ammonium cation, triethyl heptyl ammonium cation, N, N-dipropyl-N-methyl-N ethyl ammonium cation, N, N-dipropyl-N-methyl--V-pentyl ammonium cation, N, N-dipropyl-N-butyl-N-hexyl ammonium cation, N, N-dipropyl-N, N-dihexyl ammonium cation, N, N-dibutyl-N-methyl--V-pentyl ammonium cation, N, N-dibutyl-N-methyl-N-hexyl ammonium cation, tricaprylmethyl ammonium cation, N-methyl-N ethyl-N-propyl group-N-amyl group ammonium cation.
As the positively charged ion that formula (E) represents, can enumerate such as: sulfonium cation etc.In addition, as the R in described formula (E) pconcrete example, methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, decyl, dodecyl, tridecyl, tetradecyl, octadecyl etc. can be enumerated.
In addition, in water-dispersed acrylic class binder composition of the present invention, the positively charged ion of described ionic liquid is preferably selected from by containing imidazoles salt form, containing pyridine salt form, containing morpholine salt form, containing tetramethyleneimine salt form, containing piperidines salt form, ammonium salt-containing type, to contain salt form and at least one contained in the group of sulfonium salt type composition.In addition, these ionic liquids are equivalent to the positively charged ion containing previously described formula (A), (B) and (D).
In water-dispersed acrylic class binder composition of the present invention, described ionic liquid is preferably containing at least one positively charged ion be selected from the group of the cation composition represented by following formula (a) ~ (d).In addition, these positively charged ions, are included in previously described formula (A) and (B).
R in previously described formula (a) 1represent the alkyl of hydrogen or carbonatoms 1 ~ 3, the alkyl of preferred hydrogen or carbonatoms 1, R 2represent the alkyl of hydrogen or carbonatoms 1 ~ 7, the alkyl of preferred carbonatoms 1 ~ 6, the more preferably alkyl of carbonatoms 1 ~ 4.
R in previously described formula (b) 3represent the alkyl of hydrogen or carbonatoms 1 ~ 3, the alkyl of preferred hydrogen or carbonatoms 1, R 4represent the alkyl of hydrogen or carbonatoms 1 ~ 7, the alkyl of preferred carbonatoms 1 ~ 6, the more preferably alkyl of carbonatoms 1 ~ 4.
R in previously described formula (c) 5represent the alkyl of hydrogen or carbonatoms 1 ~ 3, the alkyl of preferred hydrogen or carbonatoms 1, R 6represent the alkyl of hydrogen or carbonatoms 1 ~ 7, the alkyl of preferred carbonatoms 1 ~ 6, the more preferably alkyl of carbonatoms 1 ~ 4.
R in previously described formula (d) 7represent the alkyl of hydrogen or carbonatoms 1 ~ 3, the alkyl of preferred hydrogen or carbonatoms 1, R 8represent the alkyl of hydrogen or carbonatoms 1 ~ 7, the alkyl of preferred carbonatoms 1 ~ 6, the more preferably alkyl of carbonatoms 1 ~ 4.
On the other hand, as anionic component, be then not particularly limited as long as meet the composition forming water-soluble (wetting ability) ionic liquid, can use such as: Cl -, Br -, I -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3cOO -, CF 3cOO -, CH 3sO 3 -, CF 3sO 3 -, (CN) 2n -, C 4f 9sO 3 -, C 3f 7cOO -, C 2f 5sO 3 -, C 3f 7sO 3 -, C 4f 9sO 3 -, (CH 3o) 2pO 2 -, (C 2h 5o) 2pO 2 -, CH 3oSO 3 -, C 4h 9oSO 3 -, C 2h 5oSO 3 -, n-C 6h 13oSO 3 -, n-C 8h 17oSO 3 -, CH 3(OC 2h 4) 2oSO 3 -, SCN -, HSO 4 -, CH 3c 6h 4oSO 3 -deng.Wherein, the anionic component particularly containing fluorine atom can obtain the ionic compound of low melting point, therefore preferably uses.
In addition, the water miscible judgement of ionic liquid such as can confirm as follows.
[water miscible evaluation method]
Being coupled to by ionic liquid in water (25 DEG C) makes the concentration of ionic liquid be 10 % by weight, uses stirrer to mix under rotating speed 300rpm, the condition of 10 minutes.Then, leave standstill after 30 minutes, visual being confirmed whether is separated or white casse, can not confirm that the judgement of above-mentioned phenomenon is water-soluble (wetting ability) ionic liquid.
As the concrete example of aforementioned water-soluble (hydrophily) ionic liquid, can enumerate: 1-pi-allyl-3-butyl imidazole Bromide, 1,3-diallyl imidazoles Bromide, 1,3-diallyl imidazoles Tetrafluoroborate, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium tetrafluoroborate, 1,3-methylimidazole Dimethylphosphate, 1,3-methylimidazole Methylsulfate,1-ethyl-3-methylimidazole Sulfovinate, 1-ethyl-3-methylimidazole Butyl sulphate, 1-ethyl-3-methylimidazole Dicyan amine salt, 1-ethyl-3-methylimidazole Diethyl phosphate, 1-ethyl-3-methylimidazole Sulfovinate, 1-ethyl-3-methylimidazole Hexyl sulfate,1-ethyl-3-methylimidazole Mesylate, 1-ethyl-3-methylimidazole 2-(2-methoxy ethoxy) sulfovinate, 1-ethyl-3-methylimidazole Octyl sulfate, 1-ethyl-3-methylimidazole Tetrafluoroborate, 1-ethyl-3-methylimidazole Ethyl rhodanate hydrochlorate, 1-ethyl-3-methylimidazole Tosilate,1-ethyl-3-methylimidazole Trifluoroacetate, 1-ethyl-3-methylimidazole Fluoroform sulphonate, 1-ethyl-3-methylimidazole Perfluor esilate, 1-ethyl-3-methylimidazole Perfluor propane sulfonic acid salt, 1-butyl-3-methylimidazole Iodide, 1-butyl-3-methylimidazole Mesylate,1-butyl-3-methylimidazole Methylsulfate, 1-butyl-3-methylimidazole Tetrafluoroborate, 1-butyl-3-methylimidazole Trifluoroacetate, 1-butyl-3-methylimidazole Fluoroform sulphonate, 1-hexyl-3-methylimidazole Chloride, 1-hexyl-3-methylimidazole Bromide,3-methyl isophthalic acid-octylimidazole Bromide, 1-butyl-pyridinium Tetrafluoroborate, 1-butyl-pyridinium Fluoroform sulphonate, 1-butyl-pyridinium Perfluor esilate, 1-ethylpyridine Fluoroform sulphonate, 1-butyl-3-picoline Fluoroform sulphonate,1-hexyl pyridine Chloride, 1-ethyl-3-picoline Sulfovinate, 1-ethyl-3-picoline Fluoroform sulphonate, 1-ethyl-3-picoline Perfluor esilate, 1-ethyl-3-picoline Perfluor propane sulfonic acid salt, 1-ethyl-3-picoline Perfluorobutanesulfonate,4-methyl-N-butyl-pyridinium Tetrafluoroborate, 1-ethyl-3-hydroxymethylpyridine Sulfovinate, 1-butyl-1-crassitude Fluoroform sulphonate, as architectural feature, has Cl -, Br -, I -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3COO -, CF 3COO -, CH 3SO 3 -, CF 3SO 3 -, (CN) 2N -, C 4F 9SO 3 -, C 3F 7COO -, C 2F 5SO 3 -, C 3F 7SO 3 -, C 4F 9SO 3 -, (CH 3O) 2PO 2 -, (C 2H 5O) 2PO 2 -, CH 3OSO 3 -, C 4H 9OSO 3 -, C 2H 5OSO 3 -, n-C 6H 13OSO 3 -, n-C 8H 17OSO 3 -, CH 3(OC 2H 4) 2OSO 3 -, SCN -, HSO 4 -, CH 3C 6H 4OSO 3 -Deng the material as anion component.
In addition, as the commercially available product of water-soluble (wetting ability) ionic liquid, can enumerate such as: the EMPES (1-ethyl-3-picoline that メ Le Network manufactures sulfovinate), Japanese カ ー リ ッ ト manufacture CIL-313 (N-butyl-3-picoline fluoroform sulphonate), Mitsubishi マ テ リ ア Le manufacture EtMePy-EF11 (N-ethyl-3-picoline fluoroform sulphonate), EtMePy-EF21 (N-ethyl-3-picoline perfluor esilate), EtMePy-EF31 (N-ethyl-3-picoline perfluor propanesulfonic acid salt), EtMePy-EF41 (N-ethyl-3-picoline perfluorobutanesulfonate), EMI-EF11 (N-ethyl-3-methylimidazole fluoroform sulphonate), EMI-EF21 (N-ethyl-3-methylimidazole perfluor esilate), EMI-EF31 (N-ethyl-3-methylimidazole perfluor propanesulfonic acid salt), BuPy-EF21 (N-butyl-pyridinium perfluor esilate), EtPy-EF11 (N-ethylpyridine fluoroform sulphonate) etc.
[water-insoluble (hydrophobicity) ionic liquid]
Water-insoluble (hydrophobicity) ionic liquid in the present invention refers to the melting salt (ionic compound) be in a liquid state at 25 DEG C, be not particularly limited, for the reason obtaining excellent anti-static ability, preferably use the ionic liquid comprising organic cation composition that following formula (A) ~ (E) represents and anionic component.In addition, sometimes by water-insoluble (hydrophobicity) ionic liquid referred to as ionic liquid (ionic liquid).
R in above formula (A) arepresent the alkyl of carbonatoms 4 ~ 20, a part for described alkyl can by hybrid atom MCM-41, R band R cidentical or different, representing the alkyl of hydrogen or carbonatoms 1 ~ 16, by hybrid atom MCM-41, wherein, when nitrogen-atoms has double bond, can there is not R in a part for described alkyl c.
R in above formula (B) drepresent the alkyl of carbonatoms 2 ~ 20, a part for described alkyl can by hybrid atom MCM-41, R e, R fand R gidentical or different, represent the alkyl of hydrogen or carbonatoms 1 ~ 16, a part for described alkyl can by hybrid atom MCM-41.
R in above formula (C) hrepresent the alkyl of carbonatoms 2 ~ 20, a part for described alkyl can by hybrid atom MCM-41, R i, R jand R kidentical or different, represent the alkyl of hydrogen or carbonatoms 1 ~ 16, a part for described alkyl can by hybrid atom MCM-41.
Z in above formula (D) represents nitrogen-atoms, sulphur atom or phosphorus atom, R l, R m, R nand R oidentical or different, representing the alkyl of carbonatoms 1 ~ 20, by hybrid atom MCM-41, wherein, when Z is sulphur atom, can there is not R in a part for described alkyl o.
R in above formula (E) prepresenting the alkyl of carbonatoms 1 ~ 18, can be the functional group of a part by hybrid atom MCM-41 of described alkyl.
As the positively charged ion that formula (A) represents, can enumerate such as: pyridine positively charged ion, piperidines positively charged ion, tetramethyleneimine positively charged ion, the positively charged ion with pyrroline skeleton, the positively charged ion with pyrrole skeleton, morpholine positively charged ion etc.
As concrete example, for example can enumerate: 1-ethylpyridine Cation, 1-butyl-pyridinium Cation, 1-hexyl pyridine Cation, 1-butyl-3-picoline Cation, 1-butyl-4-picoline Cation, 1-hexyl-3-picoline Cation,1-butyl-3,4-lutidines Cation, 1,1-dimethyl pyrrolidine Cation, 1-ethyl-1-crassitude Cation, 1-methyl isophthalic acid-propyl pyrrole alkane Cation, 1-methyl isophthalic acid-butyl pyrrolidine Cation, 1-methyl-1-pentene base pyrrolidines Cation,1-methyl isophthalic acid-hexyl pyrrolidines Cation, 1-methyl isophthalic acid-heptyl pyrrolidines Cation, 1-ethyl-1-propyl pyrrole alkane Cation, 1-ethyl-1-butyl pyrrolidine Cation, 1-ethyl-1-amyl group pyrrolidines Cation, 1-ethyl-1-hexyl pyrrolidines Cation,1-ethyl-1-heptyl pyrrolidines Cation, 1,1-dipropyl pyrrolidines Cation, 1-propyl group-1-butyl pyrrolidine Cation, 1,1-dibutyl pyrrolidines Cation, 1-propylpiperdine Cation, 1-amyl piperidine Cation,1,1-lupetidine Cation, 1-methyl isophthalic acid-ethyl piperidine Cation, 1-methyl isophthalic acid-propylpiperdine Cation, 1-methyl isophthalic acid-butyl piperidine Cation, 1-methyl-1-pentene phenylpiperidines Cation, 1-methyl isophthalic acid-hexyl piperidines Cation,1-methyl isophthalic acid-heptyl piperidines Cation, 1-ethyl-1-propylpiperdine Cation, 1-ethyl-1-butyl piperidine Cation, 1-ethyl-1-amyl piperidine Cation, 1-ethyl-1-hexyl piperidines Cation, 1-ethyl-1-heptyl piperidines Cation,1,1-dipropyl piperidines Cation, 1-propyl group-1-butyl piperidine Cation, 1,1-dibutyl piperidines Cation, 2-methyl isophthalic acid-pyrrolin cation, 1-ethyl-2-phenylindone cation, 1,2-dimethyl indole cation, 1-ethyl carbazole cation, N-ethyl-N-methylmorpholinium Cation.
As the positively charged ion that formula (B) represents, can enumerate such as: imidazoles positively charged ion, tetrahydropyrimidine positively charged ion, dihydro-pyrimidin positively charged ion etc.
As concrete example, can enumerate such as: 1,3-methylimidazole positively charged ion, 1,3-diethyl imidazolium positively charged ion, 1-ethyl-3-methylimidazole positively charged ion, 1-butyl-3-Methylimidazole positively charged ion, 1-hexyl-3-Methylimidazole positively charged ion, 1-octyl group-3-Methylimidazole positively charged ion, 1-decyl-3-Methylimidazole positively charged ion, 1-dodecyl-3-Methylimidazole positively charged ion, 1-tetradecyl-3-Methylimidazole positively charged ion, 1,2-dimethyl-3-propyl imidazole positively charged ion, 1-ethyl-2,3-methylimidazole positively charged ion, 1-butyl-2,3-methylimidazole positively charged ion, 1-hexyl-2,3-methylimidazole positively charged ion, 1,3-dimethyl-1,4,5,6-tetrahydrochysene pyrimidine positively charged ion, 1,2,3-trimethylammonium-Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine positively charged ion, 1,2,3,4-tetramethyl--Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine positively charged ion, 1,2,3,5-tetramethyl--Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine positively charged ion, 1,3-dimethyl-Isosorbide-5-Nitrae-dihydro-pyrimidin positively charged ion, 1,3-dimethyl-1,6-dihydro-pyrimidin positively charged ion, 1,2,3-trimethylammonium-Isosorbide-5-Nitrae-dihydro-pyrimidin positively charged ion, 1,2,3-trimethylammonium-1,6-dihydro-pyrimidin positively charged ion, 1,2,3,4-tetramethyl--Isosorbide-5-Nitrae-dihydro-pyrimidin positively charged ion, 1,2,3,4-tetramethyl--1,6-dihydro-pyrimidin positively charged ion etc.
As the positively charged ion that formula (C) represents, can enumerate such as: pyrazoles positively charged ion, pyrazoline positively charged ion etc.
As concrete example, can enumerate such as: 1-methylpyrazole positively charged ion, 3-methylpyrazole positively charged ion, 1-Ethyl-2-Methyl pyrazoles positively charged ion, 1-ethyl-2,3,5-trimethylpyrazol positively charged ion, 1-propyl group-2,3,5-trimethylpyrazol positively charged ion, 1-butyl-2,3,5-trimethylpyrazol positively charged ion, 1-ethyl-2,3,5-trimethylpyrazol quinoline positively charged ion, 1-propyl group-2,3,5-trimethylpyrazol quinoline positively charged ion, 1-butyl-2,3,5-trimethylpyrazol quinoline positively charged ion etc.
As the positively charged ion that formula (D) represents, can enumerate such as: tetraalkylammonium cation, trialkylsulfonium cation, tetraalkyl the positively charged ion etc. that the part of positively charged ion, described alkyl is replaced by thiazolinyl, alkoxyl group, hydroxyl, cyano group and epoxy group(ing).
As concrete example, can enumerate such as: tetramethylammonium cation, tetraethylammonium cation, tetrabutyl ammonium cation, four pentyl ammonium cation, tetrahexyl ammonium positively charged ion, four heptyl ammonium cations, triethyl methyl ammonium cation, tributyl ethyl ammonium cations, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium cation, glycidyltrimetiiylammonium ammonium cation, trimethylsulfonium positively charged ion, triethyl sulfonium cation, tributyl sulfonium cation, three hexyl sulfonium cations, diethylmethyl sulfonium cation, dibutylethyl sulfonium cation, tetramethyl- positively charged ion, tetraethyl- positively charged ion, the tetrabutyl positively charged ion, four hexyls positively charged ion, four octyl groups positively charged ion, triethyl methyl positively charged ion, tributyl ethyl positively charged ion, diallyl dimethyl ammonium positively charged ion etc.Wherein, preferably triethyl methyl ammonium cation, tributyl ethyl ammonium cations, diethylmethyl sulfonium cation, dibutylethyl sulfonium cation, triethyl methyl is used positively charged ion, tributyl ethyl positively charged ion, trimethyldecylammonium the asymmetrical tetraalkylammonium cation such as positively charged ion, trialkylsulfonium cation, tetraalkyl positively charged ion, or N, N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium cation, glycidyltrimetiiylammonium ammonium cation, diallyl dimethyl ammonium positively charged ion, N, N-dimethyl-N-ethyl-N-propyl ammonium positively charged ion, N, N-dimethyl-N-ethyl-N-butyl ammonium cation, N, N-dimethyl-N-ethyl-N-amyl group ammonium cation, N, N-dimethyl-N-ethyl-N-hexyl ammonium cation, N, N-dimethyl-N-ethyl-N-heptyl ammonium cation, N, N-dimethyl-N-ethyl-N-nonyl ammonium cation, N, N-dimethyl-N, N-dipropylammonium positively charged ion, N, N-diethyl-N-propyl-N-butyl ammonium cation, N, N-dimethyl-N-propyl group-N-amyl group ammonium cation, N, N-dimethyl-N-propyl group-N-hexyl ammonium cation, N, N-dimethyl-N-propyl group-N-heptyl ammonium cation, N, N-dimethyl-N-butyl-N-hexyl ammonium cation, N, N-diethyl-N-butyl-N-heptyl ammonium cation, N, N-dimethyl-N-amyl group-N-hexyl ammonium cation, N, N-dimethyl-N, N-dihexyl ammonium cation, trimethylammonium heptyl ammonium cation, N, N-diethyl-N-Methyl-N-propyl ammonium cation, N, N-diethyl-N-methyl--V-pentyl ammonium cation, N, N-diethyl-N-methyl-N-heptyl ammonium cation, N, N-diethyl-N-propyl-N-amyl group ammonium cation, triethyl propyl ammonium positively charged ion, triethyl amyl group ammonium cation, triethyl heptyl ammonium cation, N, N-dipropyl-N-methyl-N ethyl ammonium cation, N, N-dipropyl-N-methyl--V-pentyl ammonium cation, N, N-dipropyl-N-butyl-N-hexyl ammonium cation, N, N-dipropyl-N, N-dihexyl ammonium cation, N, N-dibutyl-N-methyl--V-pentyl ammonium cation, N, N-dibutyl-N-methyl-N-hexyl ammonium cation, tricaprylmethyl ammonium cation, N-methyl-N ethyl-N-propyl group-N-amyl group ammonium cation.
As the positively charged ion that formula (E) represents, can enumerate such as: sulfonium cation etc.In addition, as the R in described formula (E) pconcrete example, methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, decyl, dodecyl, tridecyl, tetradecyl, octadecyl etc. can be enumerated.
In addition, in water-dispersed acrylic class binder composition of the present invention, the positively charged ion of described ionic liquid is preferably selected from by containing imidazoles salt form, containing pyridine salt form, containing morpholine salt form, containing tetramethyleneimine salt form, containing piperidines salt form, ammonium salt-containing type, to contain salt form and at least one contained in the group of sulfonium salt type composition.In addition, these ionic liquids are equivalent to the positively charged ion containing previously described formula (A), (B) and (D).
In addition, in water-dispersed acrylic class binder composition of the present invention, described ionic liquid is preferably containing at least one positively charged ion be selected from the group of the cation composition represented by following formula (a) ~ (d).In addition, these positively charged ions are included in previously described formula (A) and (B).
R in previously described formula (a) 1represent the alkyl of hydrogen or carbonatoms 1 ~ 3, the alkyl of preferred hydrogen or carbonatoms 1, R 2represent the alkyl of hydrogen or carbonatoms 1 ~ 7, the alkyl of preferred carbonatoms 1 ~ 6, the more preferably alkyl of carbonatoms 1 ~ 4.
R in previously described formula (b) 3represent the alkyl of hydrogen or carbonatoms 1 ~ 3, the alkyl of preferred hydrogen or carbonatoms 1, R 4represent the alkyl of hydrogen or carbonatoms 1 ~ 7, the alkyl of preferred carbonatoms 1 ~ 6, the more preferably alkyl of carbonatoms 1 ~ 4.
R in previously described formula (c) 5represent the alkyl of hydrogen or carbonatoms 1 ~ 3, the alkyl of preferred hydrogen or carbonatoms 1, R 6represent the alkyl of hydrogen or carbonatoms 1 ~ 7, the alkyl of preferred carbonatoms 1 ~ 6, the more preferably alkyl of carbonatoms 1 ~ 4.
R in previously described formula (d) 7represent the alkyl of hydrogen or carbonatoms 1 ~ 3, the alkyl of preferred hydrogen or carbonatoms 1, R 8represent the alkyl of hydrogen or carbonatoms 1 ~ 7, the alkyl of preferred carbonatoms 1 ~ 6, the more preferably alkyl of carbonatoms 1 ~ 4.
On the other hand, as anionic component, be then not particularly limited as long as meet the composition forming water-insoluble (hydrophobicity) ionic liquid, can use such as: PF 6 -, CF 3sO 3 -, (CF 3sO 2) 2n -, (CF 3sO 2) 3c -, (C 2f 5sO 2) 2n -, (CF 3sO 2) (CF 3cO) N -, (FSO 2) 2n -, (C 3f 7sO 2) 2n -, (C 4f 9sO 2) 2n -, (C 2f 5) 3pF 3 -deng.Wherein, the anionic component particularly containing imide structure can obtain the ionic compound of low melting point, therefore preferably uses.
In addition, the hydrophobic judgement of ionic liquid such as can confirm as follows.
[evaluation method of water-insoluble (hydrophobicity) of ionic liquid]
Being coupled to by ionic liquid in water (25 DEG C) makes the concentration of ionic liquid be 10 % by weight, uses stirrer to mix under rotating speed 300rpm, the condition of 10 minutes.Then, leave standstill after 30 minutes, visual confirmation is separated or white casse, can confirm that the judgement of above-mentioned phenomenon is water-insoluble (hydrophobicity) ionic liquid.
As the concrete example of aforementioned water-insoluble (hydrophobicity) ionic liquid, for example can enumerate: 1-butyl-3-picoline Two (fluoroform sulphonyl) imines, 1-butyl-3-picoline Two (five fluorine second sulphonyl) imines, 1-ethyl-3-hydroxymethylpyridine Two (fluoroform sulphonyl) imines, 1,1-dimethyl pyrrolidine Two (fluoroform sulphonyl) imines, 1-methyl isophthalic acid-ethyl pyrrolidine Two (fluoroform sulphonyl) imines,1-methyl isophthalic acid-propyl pyrrole alkane Two (fluoroform sulphonyl) imines, 1-methyl isophthalic acid-butyl pyrrolidine Two (fluoroform sulphonyl) imines, 1-methyl-1-pentene base pyrrolidines Two (fluoroform sulphonyl) imines, 1-methyl isophthalic acid-hexyl pyrrolidines Two (fluoroform sulphonyl) imines, 1-methyl isophthalic acid-heptyl pyrrolidines Two (fluoroform sulphonyl) imines, 1-ethyl-1-propyl pyrrole alkane Two (fluoroform sulphonyl) imines, 1-ethyl-1-butyl pyrrolidine Two (fluoroform sulphonyl) imines, 1-ethyl-1-amyl group pyrrolidines Two (fluoroform sulphonyl) imines, 1-ethyl-1-hexyl pyrrolidines Two (fluoroform sulphonyl) imines, 1-ethyl-1-heptyl pyrrolidines Two (fluoroform sulphonyl) imines, 1,1-dipropyl pyrrolidines Two (fluoroform sulphonyl) imines,1-propyl group-1-butyl pyrrolidine Two (fluoroform sulphonyl) imines, 1,1-dibutyl pyrrolidines Two (fluoroform sulphonyl) imines, 1-propylpiperdine Two (fluoroform sulphonyl) imines, 1-amyl piperidine Two (fluoroform sulphonyl) imines, 1,1-lupetidine Two (fluoroform sulphonyl) imines, 1-methyl isophthalic acid-ethyl piperidine Two (fluoroform sulphonyl) imines,1-methyl isophthalic acid-propylpiperdine Two (fluoroform sulphonyl) imines, 1-methyl isophthalic acid-butyl piperidine Two (fluoroform sulphonyl) imines, 1-methyl-1-pentene phenylpiperidines Two (fluoroform sulphonyl) imines, 1-methyl isophthalic acid-hexyl piperidines Two (fluoroform sulphonyl) imines, 1-methyl isophthalic acid-heptyl piperidines Two (fluoroform sulphonyl) imines, 1-ethyl-1-propylpiperdine Two (fluoroform sulphonyl) imines, 1-ethyl-1-butyl piperidine Two (fluoroform sulphonyl) imines, 1-ethyl-1-amyl piperidine Two (fluoroform sulphonyl) imines, 1-ethyl-1-hexyl piperidines Two (fluoroform sulphonyl) imines, 1-ethyl-1-heptyl piperidines Two (fluoroform sulphonyl) imines, 1,1-dipropyl piperidines Two (fluoroform sulphonyl) imines,1-propyl group-1-butyl piperidine Two (fluoroform sulphonyl) imines, 1, l-dibutyl piperidines Two (fluoroform sulphonyl) imines, 1,1-dimethyl pyrrolidine Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-ethyl pyrrolidine Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-propyl pyrrole alkane Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-butyl pyrrolidine Two (five fluorine second sulphonyl) imines, 1-methyl-1-pentene base pyrrolidines Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-hexyl pyrrolidines Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-heptyl pyrrolidines Two (five fluorine second sulphonyl) imines, 1-ethyl-1-propyl pyrrole alkane Two (five fluorine second sulphonyl) imines, 1-ethyl-1-butyl pyrrolidine Two (five fluorine second sulphonyl) imines,1-ethyl-1-amyl group pyrrolidines Two (five fluorine second sulphonyl) imines, 1-ethyl-1-hexyl pyrrolidines Two (five fluorine second sulphonyl) imines, 1-ethyl-1-heptyl pyrrolidines Two (five fluorine second sulphonyl) imines, 1,1-dipropyl pyrrolidines Two (five fluorine second sulphonyl) imines, 1-propyl group-1-butyl pyrrolidine Two (five fluorine second sulphonyl) imines, 1,1-dibutyl pyrrolidines Two (five fluorine second sulphonyl) imines, 1-propylpiperdine Two (five fluorine second sulphonyl) imines, 1-amyl piperidine Two (five fluorine second sulphonyl) imines, 1,1-lupetidine Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-ethyl piperidine Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-propylpiperdine Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-butyl piperidine Two (five fluorine second sulphonyl) imines, 1-methyl-1-pentene phenylpiperidines Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-hexyl piperidines Two (five fluorine second sulphonyl) imines, 1-methyl isophthalic acid-heptyl piperidines Two (five fluorine second sulphonyl) imines, 1-ethyl-1-propylpiperdine Two (five fluorine second sulphonyl) imines, 1-ethyl-1-butyl piperidine Two (five fluorine second sulphonyl) imines,1-ethyl-1-amyl piperidine Two (five fluorine second sulphonyl) imines, 1-ethyl-1-hexyl piperidines Two (five fluorine second sulphonyl) imines, 1-ethyl-1-heptyl piperidines Two (five fluorine second sulphonyl) imines, 1,1-dipropyl piperidines Two (five fluorine second sulphonyl) imines, 1-propyl group-1-butyl piperidine Two (five fluorine second sulphonyl) imines, 1,1-dibutyl piperidines Two (five fluorine second sulphonyl) imines, 1-ethyl-3-methylimidazole Two (fluoroform sulphonyl) imines, 1-ethyl-3-methylimidazole Two (five fluorine second sulphonyl) imines, 1-ethyl-3-methylimidazole Three (fluoroform sulphonyl) methide, 1-ethyl-3-methylimidazole Two (fluoroform sulphonyl) imines, 1-butyl-3-methylimidazole Two (fluoroform sulphonyl) imines,1,2-dimethyl-3-propyl imidazole Two (fluoroform sulphonyl) imines, 1-(2-hydroxyethyl)-3-methylimidazole Two (fluoroform sulphonyl) imines, 1-pi-allyl-3-methylimidazole Two (fluoroform sulphonyl) imines, 1-ethyl-2,3,5-trimethylpyrazol Two (fluoroform sulphonyl) imines, 1-propyl group-2,3,5-trimethylpyrazol Two (fluoroform sulphonyl) imines,1-butyl-2,3,5-trimethylpyrazol Two (fluoroform sulphonyl) imines, 1-ethyl-2,3,5-trimethylpyrazol Two (five fluorine second sulphonyl) imines, 1-propyl group-2,3,5-trimethylpyrazol Two (five fluorine second sulphonyl) imines, 1-butyl-2,3,5-trimethylpyrazol Two (five fluorine second sulphonyl) imines, 1-ethyl-2,3,5-trimethylpyrazol Two (fluoroform sulphonyl) trifluoroacetamide,1-propyl group-2,3,5-trimethylpyrazol Two (fluoroform sulphonyl) trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazol Two (fluoroform sulphonyl) trifluoroacetamide, 1-ethyl-2,3,5-trimethylpyrazol quinoline Two (fluoroform sulphonyl) imines, 1-propyl group-2,3,5-trimethylpyrazol quinoline Two (fluoroform sulphonyl) imines, 1-butyl-2,3,5-trimethylpyrazol quinoline Two (fluoroform sulphonyl) imines,1-ethyl-2,3,5-trimethylpyrazol quinoline Two (five fluorine second sulphonyl) imines, 1-propyl group-2,3,5-trimethylpyrazol quinoline Two (five fluorine second sulphonyl) imines, 1-butyl-2,3,5-trimethylpyrazol quinoline Two (five fluorine second sulphonyl) imines, 1-ethyl-2,3,5-trimethylpyrazol quinoline Two (fluoroform sulphonyl) trifluoroacetamide, 1-propyl group-2,3,5-trimethylpyrazol quinoline Two (fluoroform sulphonyl) trifluoroacetamide,1-butyl-2,3,5-trimethylpyrazol quinoline two (fluoroform sulphonyl) trifluoroacetamide, two (fluoroform sulphonyl) imines of four pentyl ammonium, two (fluoroform sulphonyl) imines of tetrahexyl ammonium, two (fluoroform sulphonyl) imines of four heptyl ammoniums, two (fluoroform sulphonyl) imines of diallyl dimethyl ammonium, two (the five fluorine second sulphonyl) imines of diallyl dimethyl ammonium, N, two (fluoroform sulphonyl) imines of N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium, N, two (the five fluorine second sulphonyl) imines of N-diethyl-N-methyl-N-(2-methoxy ethyl) ammonium, two (fluoroform sulphonyl) imines of glycidyltrimetiiylammonium ammonium, two (the five fluorine second sulphonyl) imines of glycidyltrimetiiylammonium ammonium, four octyl groups two (fluoroform sulphonyl) imines, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-ethyl-N-propyl ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-ethyl-N-butyl ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-ethyl-N-amyl group ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-ethyl-N-hexyl ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-ethyl-N-heptyl ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-ethyl-N-nonyl ammonium, N, N-dimethyl-N, two (fluoroform sulphonyl) imines of N-dipropylammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-propyl group-N-butyl ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-propyl group-N-amyl group ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-propyl group-N-hexyl ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-propyl group-N-heptyl ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-butyl-N-hexyl ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-butyl-N-heptyl ammonium, N, two (fluoroform sulphonyl) imines of N-dimethyl-N-amyl group-N-hexyl ammonium, N, N-dimethyl-N, two (fluoroform sulphonyl) imines of N-dihexyl ammonium, two (fluoroform sulphonyl) imines of trimethyl heptyl ammonium,N, two (fluoroform sulphonyl) imines of N-diethyl-N-Methyl-N-propyl ammonium, N, two (fluoroform sulphonyl) imines of N-diethyl-N-methyl--V-pentyl ammonium, N, two (fluoroform sulphonyl) imines of N-diethyl-N-methyl-N-heptyl ammonium, N, two (fluoroform sulphonyl) imines of N-diethyl-N-propyl-N-amyl group ammonium, two (fluoroform sulphonyl) imines of triethyl group propyl ammonium, two (fluoroform sulphonyl) imines of triethyl group amyl group ammonium, two (fluoroform sulphonyl) imines of triethyl group heptyl ammonium, N, two (fluoroform sulphonyl) imines of N-dipropyl-N-methyl-N ethyl ammonium, N, two (fluoroform sulphonyl) imines of N-dipropyl-N-methyl--V-pentyl ammonium, N, two (fluoroform sulphonyl) imines of N-dipropyl-N-butyl-N-hexyl ammonium, N, N-dipropyl-N, two (fluoroform sulphonyl) imines of N-dihexyl ammonium, N, two (fluoroform sulphonyl) imines of N-dibutyl-N-methyl--V-pentyl ammonium, N, two (fluoroform sulphonyl) imines of N-dibutyl-N-methyl-N-hexyl ammonium, two (fluoroform sulphonyl) imines of tricaprylmethylammonium, two (fluoroform sulphonyl) imines of N-methyl-N ethyl-N-propyl group-N-amyl group ammonium, 1-butyl-pyridinium (fluoroform sulphonyl) trifluoroacetamide, 1-butyl-3-picoline (fluoroform sulphonyl) trifluoroacetamide, 1-ethyl-3-methylimidazole (fluoroform sulphonyl) trifluoroacetamide,1-methyl isophthalic acid-propyl pyrrole alkane Two (fluorine sulphonyl) imines, 1-methyl isophthalic acid-propyl pyrrole alkane Two (fluorine sulphonyl) imines, 1-methyl isophthalic acid-propylpiperdine Two (fluorine sulphonyl) imines, as architectural feature, there is two (fluoroform sulphonyl) imines, two (five fluorine second sulphonyl) imines, two (fluorine sulphonyl) imines, three (fluoroform sulphonyl) methide, (fluoroform sulphonyl) trifluoroacetamide, two (fluorine sulphonyl) imines material as anion component.
In addition, as the commercially available product of water-insoluble (hydrophobicity) ionic liquid, can enumerate such as: the CIL-312 (N-butyl-3-picoline that Japanese カ ー リ ッ ト manufactures two (fluoroform sulphonyl) imines), first industrial pharmaceutical manufacture ElexcelIL-110 (1-ethyl-3-methylimidazole two (fluorine sulphonyl) imines), ElexcelIL-120 (1-methyl isophthalic acid-propyl pyrrole alkane two (fluorine sulphonyl) imines), ElexcelIL-130 (1-methyl isophthalic acid-propylpiperdine two (fluorine sulphonyl) imines), ElexcelIL-210 (1-ethyl-3-methylimidazole two (fluoroform sulphonyl) imines), ElexcelIL-220 (1-methyl isophthalic acid-propyl pyrrole alkane two (fluoroform sulphonyl) imines), ElexcelIL-230 (1-methyl isophthalic acid-propylpiperdine two (fluoroform sulphonyl) imines) etc.
Aforesaid ionic liquid (comprising water-soluble and water-insoluble ionic liquid) can use commercially available product, also can synthesize as follows.As the synthetic method of ionic liquid, as long as object ion liquid can be obtained then to be not particularly limited, generally speaking, halide, hydroxide process, acid esters method, complexometry and neutralisation etc. of recording in document " イ オ Application liquid-development the most front Line と future-(ionic liquid-exploitation forward position and future) " (Co., Ltd. C MC publishes and distributes) can be used.
Below, about halide, hydroxide process, acid esters method, complexometry and neutralisation, with nitrogenous salt is that example is described its synthetic method, in addition, for sulfur-bearing salt, phosphorous other ionic liquid such as salt also can be obtained by same method.
Halide is the method for being undertaken by the reaction shown in following formula (1) ~ (3).First, tertiary amine and haloalkane react and obtain halogenide (reaction formula (1) uses chlorine, bromine, iodine as halogen).
Make obtained halogenide and the anion structure (A with object ion liquid -) acid (HA) or salt (MA, M are that ammonium, lithium, sodium, potassium etc. form the positively charged ion of salt with desired anion) react and obtain object ion liquid (R 4nA).
(1)R 3N+RX→R 4NX(X：CI，Br，I)
(2)R 4NX+HA→R 4NA+HX
(3) R 4nX+MA → R 4nA+MX (M:NH 4, Li, Na, K, Ag etc.)
Hydroxide process is the method for being undertaken by the reaction shown in (4) ~ (8).First, halogenide (R is made 4nX) by ion exchange membrane electrolysis (reaction formula (4)), OH type ion-exchange-resin process (reaction formula (5)) or with silver suboxide (Ag 2o) reaction (reaction formula (6)) obtains oxyhydroxide (R 4nOH) (chlorine, bromine, iodine is used as halogen).
What obtained oxyhydroxide is utilized in the same manner as aforementioned halogen process reaction formula (7) ~ (8) is obtained by reacting object ion liquid (R 4nA).
(4)R 4NX+H 2O→R 4NOH+1/2H 2+1/2X 2(X：CI，Br，I)
(5) R 4nX+P-OH → R 4nOH+P-X (P-OH:OH type ion exchange resin)
(6)R 4NX+1/2Ag 2O+1/2H 2O→R 4NOH+AgX
(7)R 4NOH+HA→R 4NA+H 2O
(8) R 4nOH+MA → R 4nA+MOH (M:NH 4, Li, Na, K, Ag etc.)
Acid esters method is the method for being undertaken by the reaction shown in (9) ~ (11).First, tertiary amine (R 3n) acid esters compound (reaction formula (9), the organic acid esters such as the ester of the mineral acids such as use sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, carbonic acid or methylsulfonic acid, methyl-phosphorous acid, formic acid etc. are as acid esters) is obtained by reacting with acid esters.
What obtained acid esters compound is utilized in the same manner as aforementioned halogen process reaction formula (10) ~ (11) is obtained by reacting object ion liquid (R 4nA).In addition, by using Methyl triflate, trifluoro-acetate etc. as acid esters, directly ionic liquid can be obtained.
(9)R 3N+ROY→R 4NOY
( deng)
(10)R 4NOY+HA→R 4NA+HOY
( when, )
(11) R 4nOY+MA → R 4nA+MOY (M:NH 4, Li, Na, K, Ag etc.)
Complexometry is the method for being undertaken by the reaction shown in (12) ~ (15).First, the halogenide (R of quaternary ammonium is made 4nX), the oxyhydroxide (R of quaternary ammonium 4nOH), the carbonic ether compound (R of quaternary ammonium 4nOCO 2cH 3) etc. with hydrogen fluoride (HF) or Neutral ammonium fluoride (NH 4f) react and obtain quaternary ammonium fluoride salt (reaction formula (12) ~ (14)).
By making obtained quaternary ammonium fluoride salt and BF 3, AlF 3, PF 5, AsF 5, SbF 5, NbF 5, TaF 5carry out complex reaction in fluorochemical, ionic liquid (reaction formula (15)) can be obtained.
(12)R 4NX+HF→R 4NF+HX(X：CI，Br，I)
(13)R 4NY+HF→R 4NF+HY(Y：OH，OCO 2CH 3)
(14)R 4NY+NH 4F→R 4NF+NH 3+HY(Y：OH，OCO 2CH 3)
(15)R 4NF+MF n-1→R 4NMF n
(MF n-1: BF 3, AlF 3, PF 5, ASF 5, SbF 5, NbF 5, TaF 5deng)
Neutralisation is the method for being undertaken by the reaction shown in (16).By making tertiary amine and HBF 4, HPF 6, CH 3cOOH, CF 3cOOH, CF 3sO 3h, (CF 3sO 2) 2nH, (CF 3sO 2) 3cH, (C 2f 5sO 2) 2the organic acid reactions such as NH can obtain.
(16)R 3N+HZ→R 3HN +Z -
[HZ：HBF 4、HPF 6、CH 3COOH、CF 3COOH、CF 3SO 3H、(CF 3SO 2) 2NH、
(CF 3sO 2) 3cH, (C 2f 5sO 2) 2the organic acids such as NH]
R in previously described formula (1) ~ (16) represents the alkyl of hydrogen or carbonatoms 1 ~ 20, can be the functional group of a part by hybrid atom MCM-41 of alkyl.
The use level of foregoing ion liquid (comprising water-soluble and water-insoluble ionic liquid) changes according to the polymkeric substance of use and the consistency of ionic liquid, therefore cannot treat different things as the same, relative to base polymer (acrylic emulsions type polymkeric substance) 100 weight parts (solids component), preferably 0.001 ~ 4.9 weight part, more preferably 0.01 ~ 3 weight part, preferably 0.03 ~ 2 weight part, most preferably 0.05 ~ 1 weight part further.During lower than 0.001 weight part, can not get sufficient antistatic characteristic, during more than 4.9 weight part, there is the tendency increased the pollution of adherend.
[an alkali metal salt]
Water-dispersed acrylic class binder composition of the present invention can be used as an alkali metal salt of ionic compound.By containing described an alkali metal salt, when peeling off after the binder layer obtained (adhesive sheet) being pasted adherend (protected object) and be upper, static electricity resistance can be given for the adherend not carrying out anti-electrostatic.In addition, described an alkali metal salt can be expected and the consistency of foregoing acrylic emulsion polymer and balanced interaction.
As an alkali metal salt of the present invention, being not particularly limited, the metal-salt such as comprising lithium, sodium, potassium can be enumerated, can preferably using such as particularly: by comprising Li +, Na +, K +positively charged ion with comprise Cl -, Br -, I -, BF 4 -, PF 6 -, SCN -, ClO 4 -, CF 3sO 3 -, (CF 3sO 2) 2n -, (C 2f 5sO 2) 2n -, (CF 3sO 2) 3c -, C 4f 9sO 3 -, CH 3cOO -, C 3h 7cOO -, (CF 3sO 2) (CF 3cO) N -, (FSO 2) 2n -, (C 4f 9sO 2) 2n -, (CH 3o) 2pO 2 -, (C 2h 5o) 2pO 2 -, (CN) 2n -, CH 3oSO 3 -, C 2h 5oSO 3 -, n-C 8h 17oSO 3 -negatively charged ion form metal-salt.Wherein, particularly as the negatively charged ion forming salt, preferably use fluorine-containing negatively charged ion.In addition, LiBr, LiI, LiBF is used 4, LiPF 6, LiSCN, LiClO 4, LiCF 3sO 3, Li (CF 3sO 2) 2n, Li (C 2f 5sO 2) 2n, Li (CF 3sO 2) 3the lithium salts such as C are optimal ways.Lithium salts shows extra high dissociative in an alkali metal salt, therefore can obtain the excellent binder layer of static electricity resistance (adhesive sheet), can as particularly requiring that the surface protective film of the optical component of static electricity resistance etc. uses.In addition, these an alkali metal salts can be used alone, and two or more may be used in combination.
About the use level of an alkali metal salt used in the present invention, relative to (methyl) acrylic polymers 100 weight part, an alkali metal salt below preferred cooperation 5 weight part, more preferably below 3 weight parts are coordinated, preferably coordinate below 2 weight parts further, most preferably coordinate 0.1 ~ 1 weight part.During more than 5 weight part, there is the tendency increased the pollution of adherend (protected object), therefore not preferred.
[oxyalkylene copolymerization]
Water-dispersed acrylic class binder composition of the present invention is preferably containing oxyalkylene copolymerization.By containing described oxyalkylene copolymerization, the ion of ionic compound can easily move between the high polyether chain of degree of freedom, can show excellent anti-static effect, therefore preferably.Specifically, polyether type defoamer, organopolysiloxane, alkyne diol type flow agent etc. can be enumerated.Wherein, particularly polyether type defoamer and organopolysiloxane due to surface tension low, even if therefore on a small quantity also there is high interfacial adsorption, therefore, it is possible to carry out interfacial adsorption under the state of ionic compound coordination, can give excellent static electricity resistance, be useful in this respect.
[polyether type defoamer]
Water-dispersed acrylic class binder composition of the present invention can contain aforementioned oxidation alkene copolymerization, the polyether type defoamer that preferred following formula (iv) represents.
HO-(PO) n1(EO) m1-H(iv)
In above formula (iv), PO represents oxygen propylidene, and EO represents oxygen ethylidene.M1 represents the integer of 0 ~ 50, and n1 represents the integer of more than 1, and m1 is preferably 1 ~ 50, more preferably 1 ~ 30, further preferably 5 ~ 20.In addition, n1 is preferably 1 ~ 200, and more preferably 10 ~ 100, further preferably 20 ~ 50.When m1 and n1 is in aforementioned range, obtain low stain, therefore preferably.In addition, the addition form of aforementioned EO and PO is random or block type.
In previously described formula (iv), PO represents oxygen propylidene, and EO represents oxygen ethylidene.N1 is the integer of more than 1, and suitably can regulate and make the PO containing ratio of polyether type defoamer be 70 ~ 100 % by weight, such as, n1 is preferably 10 ~ 69.M1 represents the integer (preferably the integer of 2 ~ 27) of 0 ~ 40.In addition, when m1 is 0, formula (iv) is HO-(PO) n1the polypropylene glycol that-H represents.
In previously described formula (iv), the addition form (copolymerized form) of EO and PO is random (random shape) or block type (block-wise).When the addition form of block type, the arrangement of each block is such as: (block be made up of EO)-(block be made up of PO)-(block be made up of EO), (block be made up of PO)-(block be made up of EO)-(block be made up of PO), (block be made up of EO)-(block be made up of PO) or (block be made up of PO)-(block be made up of EO).
In foregoing polyethers type defoamer, good especially from the viewpoint of the balance of defoaming and low stain, the compound that preferred formula (iv) represents, wherein, the addition form (copolymerized form) of EO and PO is block type (block-wise), and the arrangement of each block is preferably (block be made up of PO)-(block be made up of EO)-(block be made up of PO).That is, foregoing polyethers type defoamer preferably has the triblock copolymer of the block be made up of PO in the block both sides be made up of EO.
In addition, foregoing polyethers type defoamer is preferably the compound that following formula (v) represents.
HO-(PO) a-(EO) b-(PO) c-H(v)
In above formula (v), PO represents oxygen propylidene, and EO represents oxygen ethylidene.A and c is preferably the integer of more than 1, and more preferably a and c is 1 ~ 100, is more preferably 10 ~ 50, more preferably 10 ~ 30.A with c can mutually identical also can be mutually different.In addition, b is preferably the integer of more than 1, is more preferably 1 ~ 50, and more preferably 1 ~ 30.When a ~ c is in aforementioned range, obtain low stain, therefore preferably.
By coordinating foregoing polyethers type defoamer ((iv) and (v)) in water-dispersed acrylic class binder composition, utilizing its defoaming, the defect deriving from bubble can be eliminated.In addition, polyether type defoamer is exuded to the interface of binder layer and adherend, gives thus and peels off regulatory function, can realize gently peeling off design (can realize light stripping with low stain by the use level increasing polyether type defoamer).In addition; by using foregoing polyethers type defoamer; detailed reason is still not clear; but based on ether; can obtain and the consistency of ionic compound, acrylic emulsions type polymkeric substance etc., balanced interaction; can realize anti-electrostatic when peeling off for the adherend (protected object) not carrying out anti-electrostatic, and can obtain the surface protective film that reduces the pollution of adherend, be therefore useful.
In foregoing polyethers type defoamer, the defoamer that above formula (v) represents is the block type structure that polyethylene oxide block is positioned at molecule central part, for there is the structure of the block be made up of the PO as hydrophobic grouping at the both ends of molecule, therefore be difficult to arrange equably at liquid-vapo(u)r interface place, can defoaming be played.Have at the both ends of molecule the PEG-PPG-PEG triblock copolymer of polyethylene oxide block, polyoxyethylene and polyoxytrimethylene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock compared with PPG-PEG-PPG triblock copolymer, easily arrange equably at liquid-vapo(u)r interface place, there is the effect of stable foam.
In addition, the hydrophobicity of foregoing polyethers type defoamer ((iv) and (v)) is high, and be therefore difficult to the reason becoming the albefaction pollution produced on adherend under high humidity environment, low stain improves.When compound (particularly water miscible compound) that wetting ability is high, under high humidity environment, compound is easily dissolved in moisture and is transferred on adherend, or be exuded to the easily swelling and albefaction of compound on adherend, therefore easily cause albefaction to pollute.
" gross weight of PO " of foregoing polyethers type defoamer ((iv) and (v)) is preferably 50 ~ 95 % by weight relative to ratio [(gross weight of PO)/(gross weight of polyether type defoamer) × 100] (unit: % by weight (%)) of " gross weight of polyether type defoamer ", be more preferably 55 ~ 90 % by weight, more preferably 60 ~ 85 % by weight.Aforementioned ratio (PO containing ratio) lower than 50 % by weight time, the wetting ability of polyether type defoamer improves, and sometimes loses defoaming.In addition, when aforementioned ratio is more than 95 % by weight, the hydrophobicity of polyether type defoamer is too high, sometimes becomes the reason of flake (Ha ジ キ).Aforesaid " gross weight of polyether type defoamer " is " total amount of the weight of the whole polyether type defoamers in binder composition of the present invention ", and " gross weight of PO " is " total amount of the weight of PO contained in the whole polyether type defoamers in binder composition of the present invention ".In addition, sometimes " gross weight of PO " is called " PO containing ratio " relative to the ratio of " gross weight of polyether type defoamer ".The measuring method of PO containing ratio can be enumerated such as: NMR, chromatography (chromatography), MALDI-TOFMS (substance assistant laser desorpted ionized time-of-flight type mass spectroscopy) or TOF-SIMS (time-of-flight type secondary ion mass spectrometry).
Oxygen propylidene containing ratio (being sometimes referred to as " PO containing ratio ") in polyether type defoamer (100 % by weight) of foregoing polyethers type defoamer is 70 ~ 100 % by weight, preferably 70 ~ 95 % by weight, more preferably 80 ~ 95 % by weight, further preferably 85 ~ 95 % by weight, most preferably 90 ~ 95 % by weight.PO containing ratio lower than 70 % by weight time, to the deterioration of the contaminative of adherend.In addition, from the viewpoint of low stain, PO containing ratio is preferably less than 95 % by weight.In addition, aforesaid " PO containing ratio " is " gross weight of the PO (oxygen propylidene) in whole polyether type defoamer is relative to the ratio (% by weight) of the gross weight of whole polyether type defoamers contained in water-dispersed acrylic class binder composition of the present invention ".As the measuring method of PO containing ratio, can enumerate such as: NMR method (nucleus magnetic resonance), chromatography (chromatography), MALDI-TOFMS (substance assistant laser desorpted ionized time-of-flight type mass spectroscopy), TOF-SIMS (time-of-flight type secondary ion mass spectrometry).
The number-average molecular weight of the foregoing polyethers type defoamer in water-dispersed acrylic class binder composition (binder composition) of the present invention is preferably 1200 ~ 4000, and more preferably 1500 ~ 3500, further preferably 1750 ~ 3000.When number-average molecular weight is less than 1200, the consistency of polyether type defoamer and system (system of binder composition) is too high, therefore sometimes can not get defoaming effect and sometimes produces the pollution to adherend.On the other hand, when number-average molecular weight is more than 4000, too high with the non-compatibility of system, although therefore defoaming improves, sometimes becoming the reason of the flake when binder composition being applied to base material etc., sometimes producing the pollution to adherend.In addition, described number-average molecular weight (Mn) is the number-average molecular weight of whole polyether type defoamers contained in water-dispersed acrylic class binder composition of the present invention.Described number-average molecular weight (Mn) refers to and measures by GPC (gel permeation chromatography) number-average molecular weight obtained.Concrete measuring method can be enumerated and the same method shown in above-mentioned " measuring method of weight-average molecular weight (Mw) ".
Foregoing polyethers type defoamer can use commercially available product.As commercially available product, can enumerate such as: the trade(brand)name " プ ロ ノ Application #101P " that Japan Oil Co manufactures, " プ ロ ノ Application #183 ", " プ ロ ノ Application #201 ", " プ ロ ノ Application #202B ", " プ ロ ノ Application #352 ", " ユ ニ ル ー Block 10MS-250KB ", " ユ ニ ル ー Block 20MT-2000B ", the trade(brand)name " ア デ カ プ Le ロ ニ ッ Network L-33 " that Asahi Denka Co., Ltd. manufactures, " ア デ カ プ Le ロ ニ ッ Network L-42 ", " ア デ カ プ Le ロ ニ ッ Network L-43 ", " ア デ カ プ Le ロ ニ ッ Network L-61 ", " ア デ カ プ Le ロ ニ ッ Network L-62 " (number-average molecular weight: 2200), " ア デ カ プ Le ロ ニ ッ Network L-71 ", " ア デ カ プ Le ロ ニ ッ Network L-72 ", " ア デ カ プ Le ロ ニ ッ Network L-81 ", " ア デ カ プ Le ロ ニ ッ Network L-92 ", " ア デ カ プ Le ロ ニ ッ Network L-101 ", " ア デ カ プ Le ロ ニ ッ Network 17R-2 " (number-average molecular weight: 2000), " ア デ カ プ Le ロ ニ ッ Network 17R-3 ", " ア デ カ プ Le ロ ニ ッ Network 17R-4 " (number-average molecular weight: 2500), " ア デ カ プ Le ロ ニ ッ Network 25R-1 ", " ア デ カ プ Le ロ ニ ッ Network 25R-2 " etc.
Foregoing polyethers type defoamer can be used alone or two or more used in combination.
When coordinating foregoing polyethers type defoamer during the making of binder composition of the present invention, preferably do not use solvent and only coordinate polyether type defoamer, but, consider from viewpoints such as raising coordinating operations, polyether type defoamer can be dispersed or dissolved in all kinds of SOLVENTS and use.As aforementioned solvents, 2-Ethylhexyl Alcohol, ethylene glycol butyl ether, dipropylene glycol, ethylene glycol, propylene glycol, n-propyl alcohol, Virahol etc. can be enumerated.In these solvents, from the viewpoint of the dispersiveness in emulsion system, preferably make spent glycol.
The use level (content in water-dispersed acrylic class binder composition of the present invention) of foregoing polyethers type defoamer is preferably 0.01 ~ 5 weight part relative to acrylic emulsions type polymkeric substance 100 weight part (solids component), more preferably 0.05 ~ 3 weight part, preferred 0.2 ~ 2 weight part further, most preferably 0.5 ~ 1.5 weight part, particularly preferably 0.6 ~ 1.5 weight part.Time during aforementioned cooperation lower than 0.01 weight part, sometimes can not get sufficient defoaming (easily producing the bad order caused by air blister defect), during more than 5 weight part, easy generation adherend is polluted sometimes.
[organopolysiloxane]
Water-dispersed acrylic class binder composition of the present invention can contain aforementioned oxidation alkene copolymerization, the organopolysiloxane that preferred following formula (vi) represents.
In formula, R 1be the organic group of 1 valency, R 2, R 3and R 4for alkylidene group, R 5for hydrogen or organic group, m and n is the integer of 0 ~ 1000, to be 0, a and b when wherein m, n are different be 0 ~ 100 integer, be 0 when wherein a, b are different.
The end of aforementioned organopolysiloxane more preferably polyoxyalkylene side chain is hydroxyl.By using aforementioned organopolysiloxane, can show the static electricity resistance to adherend (protected object), be therefore effective.
About the use level of aforementioned organopolysiloxane, relative to foregoing acrylic emulsion polymer 100 weight part, preferably coordinate below 5 weight parts, more preferably coordinate 0.01 ~ 4 weight part.During more than 5 weight part, there is the tendency producing and pollute, therefore not preferred.
In addition, as aforementioned organopolysiloxane, specifically, the R in formula 1for with aryl or the illustrative monovalent organic group of the alkyl such as benzyl, styroyl such as the alkyl such as methyl, ethyl, propyl group, phenyl, tolyls, the substituting groups such as hydroxyl can be had separately.R 2, R 3and R 4the alkylidene group of the carbonatomss 1 ~ 8 such as methylene radical, ethylidene, propylidene can be used.At this, R 3and R 4for different alkylidene groups, R 2with R 3or R 4can be identical, also can be different.In order to improve the concentration of an alkali metal salt that can be dissolved in this polyoxyalkylene side chain, R 3and R 4in any one be preferably ethylidene or propylidene.R 5can be with alkyl or the illustrative monovalent organic group of the acyl group such as ethanoyl, propionyl such as methyl, ethyl, propyl group, can the substituting groups such as hydroxyl be had separately.These compounds can be used alone, and two or more may be used in combination.In addition, (methyl) acryl, allyl group, hydroxyl isoreactivity substituting group can be had in molecule.Have in the organopolysiloxane of above-mentioned polyoxyalkylene side chain, the organopolysiloxane especially with the polyoxyalkylene side chain of C-terminal infers the balance easily obtaining consistency, therefore preferably.
As the concrete example of aforementioned organopolysiloxane, such as can enumerate the trade(brand)name KF-351A as commercially available product, KF-353, KF-945, KF-6011, KF-889, KF-6004 (above for chemical industrial company of SHIN-ETSU HANTOTAI manufactures), FZ-2122, FZ-2164, FZ-7001, SH8400, SH8700, SH8410, SH8422 (above Dong Li Dow Corning Corporation manufactures), TSF-4440, TSF-4445, TSF-4452, TSF-4460 (MomentivePerformanceMaterials's manufacture), BYK-333, BYK-377, BYK-UV3500, BYK-UV3570 (manufacture of PVC ッ Network ケ ミ ー ジ ャ パ Application company) etc.These compounds can be used alone, and two or more may be used in combination.
In water-dispersed acrylic class binder composition of the present invention, in order to improve defoaming effect further, can containing the polyoxyalkylene compounds (being sometimes referred to as " other polyoxyalkylene compounds ") beyond foregoing polyethers type defoamer.As other poly (oxyalkylene) based compound aforementioned, can enumerate such as: the monohydroxy-alcohol (butanols of carbonatoms 4 ~ 18, primary isoamyl alcohol, Pentyl alcohol, hexanol, enanthol, octanol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol, pentadecanol, hexadecanol, heptadecyl alcohol and stearyl alcohol etc.), monocarboxylic acid (the butyric acid of carbonatoms 4 ~ 18, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, undeeanoic acid, lauric acid, tridecylic acid, tetradecanoic acid, pentadecanoic acid, palmitinic acid, margaric acid and stearic acid etc.) or the monoamine (butylamine of carbonatoms 4 ~ 18, octylame, lauryl amine and stearylamine etc.) with the reaction product of the oxyalkylene of carbonatoms 2 or 4, polyvalent alcohol [the glycerine of carbonatoms 3 ~ 60, TriMethylolPropane(TMP), tri hydroxy methyl butane, tetramethylolmethane, phenol or alkylphenol (octyl phenol, nonylphenol and butylphenol etc.) formaldehyde condensation products, sugar (glucosides, sucrose, isomaltulose, trehalose, isotrehalose, gentianose, melizitose, trisaccharide and raffinose etc. before car)] with the reaction product etc. of the oxyalkylene of carbonatoms 2 or 4.
The content of other poly (oxyalkylene) based compound aforementioned is preferably below 100 weight parts relative to described polyether type defoamer 100 weight part, more preferably 1 ~ 70 weight part, further preferably 3 ~ 50 weight parts, most preferably 5 ~ 30 weight parts.
From the viewpoint of low stain, in water-dispersed acrylic class binder composition of the present invention, preferably do not add the quaternary ammonium salt used as crosslinking catalyst, preferably do not add quaternary ammonium compound further.Therefore, water-dispersed acrylic class binder composition of the present invention preferably in fact not containing quaternary ammonium salt, does not preferably contain quaternary ammonium compound in fact further.These compounds are general as uses such as the reactive catalyzer for improving epoxies linking agent.But these compounds are not brought in the polymkeric substance forming binder layer, but can free migration within the adhesive layer, therefore adherend surface is easily precipitate into, time in binder composition containing these compounds, sometimes easily cause albefaction to pollute, can not low stain be realized.Specifically, the content of the quaternary ammonium salt in water-dispersed acrylic class binder composition of the present invention is preferably less than 0.1 % by weight relative to binder composition (non-volatile content) 100 % by weight, be more preferably less than 0.01 % by weight, be preferably less than 0.005 % by weight further.In addition, the content of quaternary ammonium compound preferably meets above-mentioned scope.
In addition, although preferably do not add aforementioned crosslinking catalyst, as the quaternary ammonium salt used if desired, can enumerate such as particularly: Tetramethylammonium hydroxide (TMAH), tetraethyl ammonium hydroxide, TPAOH, the alkyl ammonium hydroxides such as TBAH or its esters, aryl ammonium hydroxide or its esters such as tetraphenyl ammonium hydroxide, with tridodecylmethylammonium ammonium ion, didecyldimethyl ammonium ion, two cocodimonium ions, distearyl Dimethyl Ammonium ion, two oleyl dimethyl ammonium ions, cetyltrimethylammonium ammonium ion, stearyl trimethyl ammonium ion, Shan Yu base trimethyl ammonium ion, two (2-hydroxyethyl) ammonium ion of cocoyl, polyoxyethylene (15) cocoyl ammonium bromide ion, two (2-hydroxyethyl) ammonium ion of oil base, cocoyl Shan Yu base Dimethyl Ammonium ion, two (2-hydroxyethyl) ammonium ion of lauryl, the derivative of two (2-hydroxyethyl) ammonium ion of decyl or above-claimed cpd is as cationic alkali or its esters etc.
[linking agent]
Water-dispersed acrylic class binder composition of the present invention, by being suitably cross-linked by foregoing acrylic emulsion polymer, can obtain the more excellent binder layer such as thermotolerance, weathering resistance or adhesive sheet.As the concrete means of cross-linking method, being not particularly limited, mainly from the viewpoint of obtaining suitable cohesive force, particularly preferably using water-insoluble linking agent.As the linking agent used in the present invention, isocyanate compound, epoxy compounds, trimeric cyanamide resinoid, aziridine derivative and metal chelate compound etc. can be used.Wherein, mainly from the viewpoint of obtaining suitable cohesive force, particularly preferably use isocyanate compound or epoxy compounds.These compounds can be used alone, and also can be use mixing two or more.
[water-insoluble linking agent]
Water-insoluble linking agent of the present invention is non-water-soluble compound, for (in a part) in molecule have two or more (such as 2 ~ 6) can with the compound of the functional group of carboxyl reaction.3 ~ 5 can be preferably with the number of the functional group of carboxyl reaction in a part.Can be more with the number of the functional group of carboxyl reaction in a part, then binder composition is more crosslinked (that is, the crosslinking structure forming the polymkeric substance of binder layer becomes intensive).Therefore, can prevent binder layer from forming the wetting and spreading of rear binder layer.In addition, form the polymkeric substance of binder layer and suffer restraints, therefore can prevent the functional group in binder layer (carboxyl) from segregating to adherend face, thus the peeling force of binder layer and adherend (bounding force) through time rise.On the other hand, in a part can with the number of the functional group of carboxyl reaction more than 6 too much time, sometimes produce gel compound.
As in water-insoluble linking agent of the present invention can with the functional group of carboxyl reaction, be not particularly limited, such as epoxy group(ing), isocyanate group, carbodiimide etc. can be enumerated.Wherein, consider from reactive viewpoint, preferred epoxy group(ing).In addition, be difficult to residual and favourable to low stain thing from the unreacted reactant reactive high therefore crosslinking reaction, and can prevent due to the unreacted carboxyl in binder layer cause with the peeling force of adherend (bounding force) through time the viewpoint that rises consider, preferred glycidyl-amino.That is, as water-insoluble linking agent of the present invention, preferably there is the epoxies linking agent of epoxy group(ing), wherein, preferably there is the linking agent (glycidyl-amino class linking agent) of glycidyl-amino.In addition, when water-insoluble linking agent of the present invention is epoxies linking agent (particularly glycidyl-amino class linking agent), the number of the epoxy group(ing) (particularly glycidyl-amino) in a part is more than 2 (such as 2 ~ 6), preferably 3 ~ 5.
Water-insoluble linking agent of the present invention is non-water-soluble compound.In addition, " water-insoluble " refers to that the solubleness (can be dissolved in the weight of the compound (linking agent) in 100 weight parts waters) in water 100 weight part of 25 DEG C is below 5 weight parts, preferably below 3 weight parts, further preferably below 2 weight parts.By using non-water-soluble linking agent, uncrosslinked and residual linking agent is difficult to the reason becoming the albefaction pollution produced on adherend under high humidity environment, and low stain improves.When water-soluble cross-linker, under high humidity environment, residual linking agent is dissolved in moisture and is easily transferred on adherend, therefore easily causes albefaction to pollute.In addition, water-insoluble linking agent is compared with water-soluble cross-linker, higher to the contribution of crosslinking reaction (with the reaction of carboxyl), prevent peeling force (bounding force) through time rise effect higher.In addition, the reactivity of the crosslinking reaction of water-insoluble linking agent is high, therefore carries out rapidly in aging middle crosslinking reaction, can prevent from causing due to the unreacted carboxyl in binder layer with the peeling force of adherend (bounding force) through time rise.In addition, the solubleness of aforementioned crosslinking agent in water such as can measure as follows.
[measuring method of the solubleness in water]
The water (25 DEG C) of identical weight and linking agent used agitator to mix under rotating speed 300rpm, the condition of 10 minutes, be divided into aqueous phase and oil phase by centrifugation.Then, water intaking, 120 DEG C of dryings 1 hour, is obtained the non-volatile content (weight part relative to the nonvolatile component of 100 weight parts waters) in aqueous phase by weight loss on drying.
Specifically, as water-insoluble linking agent of the present invention, can illustrate: 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene is (such as, Mitsubishi Gas Chemical Co., Ltd manufactures, trade(brand)name " TETRAD-C " etc.) [solubleness in water 100 weight part of 25 DEG C is below 2 weight parts], 1, two (the N of 3-, N-diglycidyl amino methyl) benzene is (such as, Mitsubishi Gas Chemical Co., Ltd manufactures, trade(brand)name " TETRAD-X " etc.) the glycidyl-amino class linking agent such as [solubleness in water 100 weight part of 25 DEG C is below 2 weight parts], three (2,3-epoxypropyl) isocyanuric acid ester is (such as, Nissan Chemical Ind Ltd manufactures, trade(brand)name " TEPIC-G " etc.) other epoxies linking agent etc. such as [solubleness in water 100 weight part of 25 DEG C is below 2 weight parts].In addition, these water-insoluble linking agents can be used alone, and two or more may be used in combination.
The use level (content in water-dispersed acrylic class binder composition of the present invention) of water-insoluble linking agent of the present invention is preferably following use level: the carboxyl 1 mole containing carboxyl unsaturated monomer (ii) used relative to the starting monomer as acrylic emulsions type polymkeric substance of the present invention, water-insoluble linking agent of the present invention can be 0.1 ~ 1.3 mole with the mole number of the functional group of carboxyl reaction, be more preferably the use level of 0.2 ~ 1.3 mole.Namely, " whole of the present invention water-insoluble linking agents can with the total mole number of the functional group of carboxyl reaction " be preferably 0.1 ~ 1.3 relative to ratio [can with the functional group/carboxyl of carboxyl reaction] (mol ratio) of " total mole numbers of whole carboxyls containing carboxyl unsaturated monomer (ii) that the starting monomer as acrylic emulsions type polymkeric substance of the present invention uses ", more preferably 0.2 ~ 1.3, further preferably 0.3 ~ 1.1, further preferably 0.3 ~ 1.0.By [can with the functional group/carboxyl of carboxyl reaction] be set as more than 0.1, the unreacted carboxyl in binder layer can be reduced, effectively prevent from resulting from carboxyl and adherend interactional through time peeling force (bounding force) rise, therefore preferably.In addition, easily the insoluble component content of solvent of the acrylic adhesives film after crosslinked and elongation at break are controlled in the scope specified in the present invention, therefore preferably.In addition, by being set as less than 1.3, the unreacted water-insoluble linking agent in binder layer can be reduced, suppressing the bad order because water-insoluble linking agent causes, improve appearance characteristics, therefore preferably.
Particularly, when water-insoluble linking agent of the present invention is epoxies linking agent, [epoxy group(ing)/carboxyl] (mol ratio) is preferably 0.2 ~ 1.3, more preferably 0.3 ~ 1.1, and further preferably 0.3 ~ 1.0.In addition, when water-insoluble linking agent of the present invention is glycidyl-amino class linking agent, [glycidyl-amino/carboxyl] (mol ratio) preferably meets aforementioned range.
In addition, such as, when in binder composition, interpolation (cooperation) 4g can be the water-insoluble linking agent of 110 (g/ equivalents) with the functional equivalent of the functional group of carboxyl reaction, what water-insoluble linking agent had such as can calculate as follows with the mole number of the functional group of carboxyl reaction.
Water-insoluble linking agent have can with the mole number of the functional group of carboxyl reaction=[use level (addition) of water-insoluble linking agent]/[functional equivalent]=4/110
Such as, as water-insoluble linking agent, when interpolation (cooperation) 4g epoxy equivalent (weight) is the epoxies linking agent of 110g/ equivalent, the mole number of the epoxy group(ing) that epoxies linking agent has such as can calculate as follows.
Mole number=[use level (addition) of epoxies linking agent]/[epoxy equivalent (weight)]=4/110 of the epoxy group(ing) that epoxies linking agent has
Water-dispersed acrylic class binder composition of the present invention can containing the linking agent (other linking agent) beyond aforementioned water-insoluble linking agent.As other linking agent, be not particularly limited, preferred multifunctional hydrazides class linking agent.By using multifunctional hydrazides class linking agent, the releasable of the binder layer formed by binder composition, binding property (tackiness) and the anchoring with supporter (base material) can be improved.Multifunctional hydrazides class linking agent (sometimes referred to as " hydrazides class linking agent ") has the compound of at least two hydrazide groups for (in a part) in molecule.The number of the hydrazide group in a part preferably 2 or 3, more preferably 2.As the compound being used as such hydrazides class linking agent, be not particularly limited, can preferably enumerate such as: careless acid dihydrazide, acid dihydrazide, amber acid dihydrazide, glutaric, adipic dihydrazide, pimelic acid two hydrazides, suberic acid two hydrazides, nonane diacid two hydrazides, sebacic dihydrazide, dodecanedioic acid two hydrazides, O-phthalic acid dihydrazide, isophthalic dihydrazide, terephthaldehyde's acid dihydrazide, 2, 6-naphthalic acid two hydrazides, naphthalic acid two hydrazides, acetonedicarboxylic acid two hydrazides, fumaric acid two hydrazides, Malaysia acid dihydrazide, methylene-succinic acid two hydrazides, trimellitic acid two hydrazides, 1, 3, 5-benzene tricarboxylic acid two hydrazides, pyromellitic acid two hydrazides, the dihydrazide compounds such as aconitic acid two hydrazides.Wherein, particularly preferably adipic dihydrazide, sebacic dihydrazide.These hydrazides class linking agents can be used alone, and also can be used in combination.
Aforementioned hydrazides class linking agent can use commercially available product, " adipic dihydrazide (reagent) " that " adipic dihydrazide (reagent) " that Tokyo HuaCheng Industry Co., Ltd such as can be used to manufacture, Wako Pure Chemical Industries, Ltd. manufacture etc.
The ketone group 1 mole of the ketone group containing unsaturated monomer that the use level (content in water-dispersed acrylic class binder composition of the present invention) of aforementioned hydrazides class linking agent uses relative to the starting monomer as acrylic emulsions type polymkeric substance, preferably 0.025 ~ 2.5 mole, more preferably 0.1 ~ 2 mole, preferably 0.2 ~ 1.5 mole further.When use level is less than 0.025 mole, the effect that linking agent adds is little, binder layer or adhesive sheet re-separation, and forms residual low molecular weight composition in the polymkeric substance of binder layer, and the albefaction sometimes easily producing adherend is polluted.In addition, during more than 2.5 moles, unreacted crosslinker component becomes the reason of pollution sometimes.
[water-dispersed acrylic class binder composition]
Water-dispersed acrylic class binder composition (binder composition) of the present invention, as mentioned above, containing acrylic emulsions type polymkeric substance of the present invention and ionic compound as neccessary composition.In addition, other various additive can be contained as required.
In addition, in water-dispersed acrylic class binder composition of the present invention, beyond reactivity (polymerizable) composition in the polymkeric substance forming binder layer, so-called non-reacted (non-polymerizable) composition (but, volatilized by drying thus do not remain except the compositions such as water within the adhesive layer) is not preferably in fact brought into containing react (polymerization) with the starting monomer etc. of acrylic emulsions type polymkeric substance.Non-reacted component residue within the adhesive layer time, these compositions are transferred on adherend sometimes, thus become albefaction pollute reason.In addition, " not containing in fact " refers to except situation about being inevitably mixed into, the situation of initiatively not adding, specifically, the content of these non-reacted compositions in binder composition (nonvolatile component) is preferably less than 1 % by weight, be more preferably less than 0.1 % by weight, be preferably less than 0.005 % by weight further.
As described non-reacted composition, can enumerate such as: the phosphate compounds etc. used in Japanese Unexamined Patent Publication 2006-45412 publication is exuded to adhesive layer surface and gives the composition etc. of separability.In addition, the non-reacted emulsifying agent such as Sodium Lauryl Sulphate BP/USP, Texapon Special can be enumerated.
In addition, water-dispersed acrylic class binder composition of the present invention can containing the various additives beyond aforementioned in the scope not affecting contaminative.As various additive, can enumerate such as: pigment, weighting agent, flow agent, dispersion agent, softening agent, stablizer, antioxidant, UV light absorber, ultra-violet stabilizer, antiaging agent, sanitas etc.
As the blending means of water-dispersed acrylic class binder composition of the present invention, known usual emulsion blending means can be used, be not particularly limited, such as, preferably use the stirring of agitator.Agitation condition is not particularly limited, and such as, temperature is preferably 10 ~ 50 DEG C, more preferably 20 ~ 35 DEG C.Churning time is preferably 5 ~ 30 minutes, more preferably 10 ~ 20 minutes.Mixing speed is preferably 10 ~ 3000rpm, more preferably 30 ~ 1000rpm.
[the insoluble component content of solvent of the acrylic adhesives film after crosslinked]
Being coated with water-dispersed acrylic class binder composition of the present invention makes dried thickness be 50 μm, then 120 DEG C of dryings 2 minutes, again at 50 DEG C of aging three days and insoluble component contents of solvent (gel fraction) of film (" crosslinked after acrylic adhesives film " or sometimes referred to as " film ") of making, from the viewpoint of low stain or raising releasable, be preferably more than 90% (% by weight), more preferably more than 95 % by weight.When the insoluble component content of solvent of film is more than 90 % by weight, binder composition cross-links to fully high degree of crosslinking, therefore when forming binder layer (adhesive sheet), can decreasing pollution thing to the transfer printing on adherend, albefaction can be suppressed to pollute.In addition, suppress re-separation, improve releasable.The higher limit of the insoluble component content of solvent of film is not particularly limited, and such as preferably 99 % by weight.In addition, aforementioned crosslinked after the insoluble component content of solvent of acrylic adhesives film can be measured by the method that the measuring method of the insoluble component content of solvent with aforesaid acrylic emulsions type polymkeric substance is same.Specifically, can be measured by the method " the acrylic emulsions type polymkeric substance " in aforesaid " measuring method of the insoluble component content of solvent " being replaced with " the acrylic adhesives film after crosslinked ".
Being coated with water-dispersed acrylic class binder composition of the present invention makes dried thickness be 50 μm, then 120 DEG C of dryings 2 minutes, elongation at break (being sometimes referred to as " breaking point elongation ") again at 50 DEG C of aging 3 days and make 23 DEG C of film (crosslinked after acrylic adhesives film) is less than 160%, preferably 40 ~ 120%, more preferably 60 ~ 115%.The standard of the degree of crosslinking of film when aforementioned elongation at break (breaking point elongation) is for making binder composition cross-links, if be less than 160%, then the crosslinking structure forming the polymkeric substance of binder layer becomes tight.Therefore, the wetting and spreading of the binder layer after can preventing binder layer from being formed.In addition, form the polymkeric substance of binder layer and suffer restraints, therefore can prevent the functional group in binder layer (carboxyl) from segregating to adherend face, thus with the peeling force (bounding force) of adherend through time rise.
In addition, aforementioned crosslinked after 23 DEG C of acrylic adhesives film at elongation at break (breaking point elongation) can stretching test measurement be passed through.Be not particularly limited, specifically, such as, by by film volume circle, columned sample (long 50mm, sectional area (floorage) 1mm can be made 2), use tensile testing machine, 23 DEG C, under the environment of 50%RH, under the condition of initial length (chuck spacing) 10mm, draw speed 50mm/ minute, carry out tension test, and the elongation measuring breaking point is obtained.
Aforementioned crosslinked after acrylic adhesives film more specifically such as can make according to following " making of the acrylic adhesives film after crosslinked ".
[making of the acrylic adhesives film after crosslinked]
Being applied to by water-dispersed acrylic class binder composition of the present invention on suitable stripping film makes dried thickness be 50 μm, then, 120 DEG C of dryings 2 minutes in Hotaircirculatingoven, carry out maintenance (aging) in three days at 50 DEG C again, make the cross linking membrane (the acrylic adhesives film after crosslinked) of water-dispersed acrylic class binder composition of the present invention.As described stripping film, be not particularly limited, such as surface can be used through the PET film of polysiloxane process, as commercially available product, can to enumerate " MRF38 " that Mitsubishi Plastics Inc manufactures.
[binder layer, adhesive sheet]
Binder layer of the present invention (adhesive sheet) is formed by aforementioned releasable water-dispersed acrylic class binder composition.The formation method of binder layer is not particularly limited, and can use known usual binder layer formation method.The formation of binder layer can be formed by drying after supporter (base material) or the described binder composition of the upper coating of stripping film (release liner).In addition, stripping (demoulding) film forms binder layer, described binder layer is pasted and is transferred on supporter (base material).
During the formation of described binder layer (adhesive sheet), described dry time temperature be generally about 80 ~ about 170 DEG C, preferably 80 ~ 160 DEG C, time of drying is about 0.5 ~ about 30 minute, preferably 1 ~ 10 minute.Further, maintenance (aging) 1 day ~ 1 week at room temperature ~ about 50 DEG C further, thus make described binder layer (adhesive sheet).
In the painting process of described binder composition, various method can be used.Specifically, can enumerate such as: the coating of roller coat, touch roll, intaglio plate coating, reversion coating, roller brush, spraying, immersion roller coat cloth, scraper coating, scraper for coating, airblade coating, curtain coating, die lip formula are coated with, utilize the methods such as the extrusion coating methods of die coater etc.
The thickness (after dry thickness) of aforementioned adhesion oxidant layer is generally about 1 ~ about 100 μm, preferably 5 ~ 50 μm, is preferably set to further in the scope of 10 ~ 40 μm.
As the constituent material of described stripping film, can enumerate such as: the sheet-like article etc. that the porous materials such as the plastics films such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, paper, cloth, non-woven fabrics, reticulation, foamed sheet, tinsel and their layered product etc. are suitable, excellent from the viewpoint of surface smoothness, preferably use plastics film.
As described plastics film; as long as the film of described binder layer can be protected then to be not particularly limited, can enumerate such as: polyethylene film, polypropylene film, polybutene film, polybutadiene membrane, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer film, pet film, polybutylene terephthalate film, polyurethane film, vinyl-vinyl acetate copolymer film etc.
The thickness of described stripping film, is generally about 5 ~ about 200 μm, preferably about 5 ~ about 100 μm.
Described stripping film can utilize polysiloxane-based, fluorine-containing type, chain alkyl class or fatty acid acyl amine releasing agent, SiO 2 powder etc. to carry out the demoulding and the anti-electrostatic process such as antifouling process and application type, kneading type, evaporation type as required.Particularly, suitably carry out polysiloxane process, chain alkyl process, fluorine-containing process etc. by the surface at described stripping film and peel off (demoulding) process, the separability from described binder layer can be improved further.
When described binder layer exposes, binder layer can be protected with stripping film before being supplied to practical application.In addition, described stripping film can directly use as the partition of adhesive optical film, can simplify in operation.
The insoluble component content of solvent (gel fraction) of aforementioned adhesion oxidant layer with aforementioned crosslinked after acrylic adhesives film in the same manner as be preferably more than 90% (% by weight), more preferably more than 95 % by weight.
Elongation at break (breaking point elongation) at 23 DEG C of aforementioned adhesion oxidant layer is preferably less than 160% in the same manner as the acrylic adhesives film after aforementioned being cross-linked, more preferably 40 ~ 160%, further preferably 40 ~ 150%, further preferably 60 ~ 150%, particularly preferably 40 ~ 120%, most preferably 60 ~ 115%.
In addition, the second-order transition temperature (Tg) forming the acrylic polymers (after crosslinked) of aforementioned adhesion oxidant layer is preferably-70 DEG C ~-10 DEG C, more preferably-70 DEG C ~-20 DEG C, preferred-70 DEG C ~-40 DEG C further, most preferably-70 DEG C ~-50 DEG C.When second-order transition temperature exceedes-10 DEG C, bounding force is insufficient sometimes, thus tilts in generations such as adding man-hour or peel off.In addition, during lower than-70 DEG C, likely re-separation in the scope of peeling rate (draw speed) more at a high speed, thus operating efficiency declines.The second-order transition temperature forming the polymkeric substance (after crosslinked) of this bonding coat such as can be regulated by monomer composition when preparing acrylic emulsions type polymkeric substance of the present invention.
By arranging aforesaid binder layer (binder layer formed by water-dispersed acrylic class binder composition of the present invention) at least one side of supporter (also referred to as " base material " or " support base material "), the adhesive sheet (adhesive sheet of band base material can be obtained; There is the adhesive sheet of the binder layer formed by water-dispersed acrylic class binder composition of the present invention) at least one side side of base material.In addition, the binder layer formed by water-dispersed acrylic class binder composition of the present invention can use as the adhesive sheet without base material himself.In addition, sometimes the adhesive sheet of aforementioned strip base material is called " adhesive sheet of the present invention " below.
Adhesive sheet of the present invention (adhesive sheet of aforementioned strip base material) such as by water-dispersed acrylic class binder composition of the present invention being applied to the surface of at least one side side of supporter (base material), and can carrying out drying and forms binder layer at least one side side of supporter and obtain (direct method) as required.Being cross-linked can by carrying out adhesive sheet heating etc. after the dehydration in drying process, drying.In addition, first binder layer can be set on stripping film, then binder layer be transferred on supporter, obtain adhesive sheet (transfer printing) thus.Be not particularly limited, binder layer is arranged preferably by so-called direct method binder composition being coated directly onto supporting body surface.The insoluble component content of solvent of binder layer of the present invention is high, therefore sometimes can not get the sufficient anchoring (adhesivity) with supporter by transfer printing.
As the supporter (base material) of adhesive sheet of the present invention, from the viewpoint of obtaining the adhesive sheet with high transparent, preferred plastic basis material (such as, plastics film or plastic sheet).As the material of plastic basis material, be not particularly limited, the such as transparent resin such as the polyester such as the polyolefine such as polypropylene, polyethylene (polyolefin resin), polyethylene terephthalate (PET) (polyester resin), polycarbonate, polymeric amide, polyimide, acrylic resin, polystyrene, cellulose acetate, polyethersulfone, triacetyl cellulose can be used.These resins can be used alone or in combination of two or more.In aforementioned substrates, be not particularly limited, preferred polyester resinoid, polyolefin resin, in addition, from the viewpoint of productivity, formability, preferably use PET, polypropylene and polyethylene.That is, as supporter (base material), preferred polyester class film or polyolefins film, further preferred PET film, polypropylene film or polyethylene film.As aforementioned polypropylene, be not particularly limited, the polypropylene as the homopolymerization type of homopolymer, the random as alpha-olefin random copolymers, the block type as 'alpha '-olefin block copolymers can be enumerated.As polyethylene, Low Density Polyethylene (LDPE), high density polyethylene(HDPE) (HDPE), linear low density polyethylene (L-LDPE) can be enumerated.These materials can be used alone, and two or more may be used in combination.
The thickness of described supporter is not particularly limited, preferably 10 ~ 150 μm, more preferably 30 ~ 100 μm.
In addition, on the surface arranging the side of binder layer of described supporter, in order to improve the adhesive power etc. with binder layer, preferably implement the easy gluing process such as acid treatment, alkaline purification, primary coat process, corona treatment, Cement Composite Treated by Plasma, UV treatment.In addition, between supporter and binder layer, can middle layer be set.The thickness in this middle layer such as preferably 0.01 ~ 1 μm, more preferably 0.05 ~ 1 μm, preferably 0.1 ~ 1 μm further.
Adhesive sheet of the present invention can be formed as coiling body, can be wound as drum under the state protecting binder layer with stripping film (partition).In addition, the back side (with the surface of opposition side, side arranging binder layer) of adhesive sheet can utilize polysiloxane-based, fluorine-containing type, chain alkyl class or fatty acid acyl amine releasing agent, SiO 2 powder etc. implement demoulding process and/or antifouling process, back side processing layer (demoulding processing layer, antifouling processing layer etc.) also can be set.As adhesive sheet of the present invention, the wherein form of preferred adhesive layer/supporter/back side processing layer.
In addition, adhesive sheet of the present invention more preferably implements anti-electrostatic process.As described anti-electrostatic process, general anti-electrostatic treatment process can be used, be not particularly limited, such as, can be used in the supporter back side (with the surface of binder layer opposition side) arrange antistatic backing method, in supporter the method for kneading kneading type antistatic agent.
As the method arranging antistatic backing, the method etc. of coating antistatic agent or the static electricity resistance resin containing antistatic agent and resinous principle, the method for conductive resin composition containing conductive material and resinous principle or electric conductive polymer, evaporation or plated conductive material can be enumerated.
As described antistatic agent, can enumerate: quaternary ammonium salt, pyridine salt etc. have the cationic antistatic agent of cationic functional group (such as, primary amino, secondary amino group, uncle's amino etc.); Sulfonate or sulfuric acid, phosphonate, phosphate ester salt etc. have the anionic antistatic agent of anionic property functional group; The amphoteric ion type antistatic agents such as alkyl betaine and derivative, imidazoline and its derivative, L-Ala and derivative thereof; The non-ionic antistatic agent such as amino alcohol and derivative, glycerine and derivative thereof, polyoxyethylene glycol and derivative thereof; And will there is the monomer polymerization of the ionic conductivity group shown in described cationic antistatic agent, anionic antistatic agent, amphoteric ion type antistatic agent or copolymerization and the ionic-conductive polymer obtained.
Specifically; as described cationic antistatic agent, the diallyl amine multipolymer etc. that styrene copolymer, diallyl dimethyl ammoniumchloride etc. that (methyl) acrylic ester polymer, polyvinyl benzyl trimethyl ammonium chloride etc. that alkyl trimethyl ammonium salt, amidopropyl trimethyl ammonium methyl sulfate salt, alkyl benzyl methyl ammonium salt, acyl group choline chloride 60, polymethyl acrylic acid dimethylaminoethyl etc. have a quaternary ammonium group have a quaternary ammonium group have quaternary ammonium group can be enumerated.As described anionic antistatic agent, can enumerate alkylsulfonate, alkylbenzene sulfonate, alkyl sulfuric ester salt, AES salt, alkyl phosphate salt, containing sulfonic styrene copolymer etc.As described amphoteric ion type antistatic agent, alkyl betaine, alkyl imidazole can be enumerated trimethyl-glycine, carboxybetaine graft copolymer etc.As described non-ionic antistatic agent, lipid acid hydroxyalkyl amide, two (2-hydroxyethyl) alkylamine, polyoxyethylene, glycerin fatty acid ester, Polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl phenyl ether, polyethylene oxide alkyl ethers, polyoxyethylene glycol, polyethylene oxide diamine, the multipolymer be made up of polyethers, polyester and polymeric amide, methoxy poly (ethylene glycol) (methyl) acrylate etc. can be enumerated.
As described electric conductive polymer, polyaniline, polypyrrole, Polythiophene etc. can be enumerated.
As described conductive material, stannic oxide, weisspiessglanz, Indium sesquioxide, Cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold and silver, copper, aluminium, nickel, chromium, titanium, iron, cobalt, cupric iodide and their alloy or mixture etc. can be enumerated.
As described resinous principle, the resins for universal use such as polyester, acrylic resin, polyvinyl resin, urethane, melamine resin, epoxy resin can be used.In addition, when antistatic agent is polymer-type antistatic agent, in static electricity resistance resin, described resinous principle can not be contained.In addition, can contain as the methylolation of linking agent or compound, epoxy compounds, the isocyanate ester compound such as melamine class, ureas, oxalic dialdehyde class, acrylic amide of hydroxyalkylation in antistatic resin.
As the method being formed described antistatic backing by coating, can enumerate described static electricity resistance resin, electric conductive polymer, conductive resin composition organic solvent or water equal solvent or dispersion medium dilution, by this coating solution on supporter (base material), and the method for drying.As described organic solvent, methylethylketone, acetone, ethyl acetate, tetrahydrofuran (THF), dioxane, pimelinketone, normal hexane, toluene, dimethylbenzene, methyl alcohol, ethanol, n-propyl alcohol, Virahol etc. can be enumerated.These solvents can be used alone or multiple combination uses.About coating process, known coating process can be used, roller coat, intaglio plate coating, reversion coating, roller brush, spraying, airblade coating, dipping or curtain coating method can be enumerated particularly.
The thickness of the antistatic backing (static electricity resistance resin layer, conductive polymer layer, conductive resin composition layer) formed by described coating is preferably 0.001 ~ 5 μm, more preferably 0.005 ~ 1 μm.
The evaporation of described conductive material or the method for plating, can enumerate vacuum evaporation, sputtering, ion plating, chemical vapor deposition, spray-wall interaction, electroless plating, electrochemical plating etc.
The thickness of the antistatic backing (conductive material layer) formed by described evaporation or plating is preferably (0.002 ~ 1 μm), more preferably (0.005 ~ 0.5 μm).
As described kneading type antistatic agent, can suitably use described antistatic agent.The use level of described kneading type antistatic agent is preferably less than 20 % by weight relative to the gross weight (100 % by weight) of supporter (base material), and more preferably 0.05 ~ 10 % by weight.As kneading process, as long as described kneading type antistatic agent can be mixed into equably in the resin being such as used as plastic basis material, then be not particularly limited, generally can enumerate the method etc. using warming mill, banbury mixers, pressure kneader, twin screw muller etc.
Water-dispersed acrylic class binder composition of the present invention for can be formed static electricity resistance, tackiness and releasable (easy separability) excellent, can peel off again the binder composition of binder layer, be preferred for forming the binder layer (peeling off use again) for peeling off purposes again.Namely, the adhesive sheet with the binder layer formed by water-dispersed acrylic class binder composition of the present invention is preferred for peeling off purposes again [such as, building maintenance masking tape, painting dressing automobiles masking tape, electronic unit (lead frame, printed base plate etc.) use masking tape, the masking tape classes such as sandblasting masking tape, aluminium windowframe surface protective film, optical plastics protective film, opticglass surface protective film, automobile protection surface protective film, the surface protective film classes such as metal sheet surface protective film, grinding back surface adhesive tape, film (ペ リ Network Le) adhesive tape for fixing, rubber belt for cutting, lead frame attachment adhesive tape, cleaning adhesive tape, dedusting adhesive tape, carrier band, the semi-conductors such as cover tape, electronic unit manufacturing process pressure-sensitive adhesive tape, the packaging adhesive tape class of electronics and electronic unit, temporary transient fixation adhesive tape class during transport, tie up and use adhesive tape class, labels class] etc.
The binder layer formed by water-dispersed acrylic class binder composition of the present invention and adhesive sheet of the present invention, bad orders such as " depressions " reduces, and appearance characteristics is excellent.In addition, paste adherend uses time, can not produce the pollutions such as albefaction pollution on adherend, low stain is excellent.Therefore, as formation, adhesive sheet of the present invention preferably particularly requires that the surface protection purposes (surface protective film etc. of optical component) of the optical component (optical plastics, opticglass, optical thin film etc.) such as polarizing plate, polarizer, antireflection plate, wavelength plate, optical compensating film, brightness enhancement film of the panel of the liquid-crystal display of excellent appearance characteristics and low stain, organic electroluminescent (organic EL), field-emitter display etc. uses.But purposes is not limited to these, surface protection when also may be used for the manufacture of the microfabrication parts such as semi-conductor, circuit, various printed base plate, various mask, lead frame or the removing of prevent breakage or foreign matter etc., to cover.
Embodiment
Below, illustrate in greater detail the present invention based on embodiment, but the present invention is not limited to the examples.In addition, in the following description, except as otherwise noted, " part " and " % " is weight basis.In addition, about evaluation, 1st ~ 3 invention groups shown below are divided into evaluate respectively.
< first invention group >
< embodiment 1-1>
(preparation of acrylic emulsions type polymkeric substance)
(Di-ichi Kogyo Seiyaku Co., Ltd. manufactures for hydrous water 90 weight part and 2-EHA as shown in table 1 (2EHA) 94 weight part, methyl methacrylate (MMA) 2 weight part, vinylformic acid (AA) 4 weight part, reactive non-ionic anion type emulsifying agent in a reservoir, trade(brand)name " ア Network ア ロ Application HS-10 ") 6 weight parts, then be uniformly mixed with super mixer, prepare monomer emulsion.Then, in the reaction vessel with prolong, nitrogen introducing tube, thermometer and agitator, add in the monomer emulsion of water 50 weight part, polymerization starter (ammonium persulphate) 0.01 weight part and above-mentioned preparation the amount being equivalent to 10 % by weight, while stirring, carry out letex polymerization in 1 hour at 75 DEG C.Then, then add polymerization starter (ammonium persulphate) 0.07 weight part, then while stirring, added remaining whole monomer emulsion (being equivalent to the amount of 90 % by weight) with 3 hours, then 75 DEG C of reactions 3 hours.Then, be cooled to 30 DEG C, the ammoniacal liquor adding concentration 10 % by weight is adjusted to pH8, the aqueous dispersions of preparation acrylic emulsions type polymkeric substance.
(preparation of water-dispersed acrylic class binder composition)
In the aqueous dispersions of the aforementioned acrylic emulsions type polymkeric substance obtained, relative to acrylic emulsions type polymkeric substance (solids component) 100 weight part, use agitator 23 DEG C, 300rpm, be uniformly mixed ionic liquid [CIL-313 that Japanese カ ー リ ッ ト Co., Ltd. manufactures, N-butyl-3-picoline under the agitation condition of 10 minutes fluoroform sulphonate (water soluble ion liquid)] 2 weight parts, as water-insoluble linking agent epoxies linking agent [Mitsubishi Gas Chemical Co., Ltd manufacture, trade(brand)name " TETRAD-C ", 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, epoxy equivalent (weight): 110, functional group number: 4] 3 weight parts, then [filter paper Co., Ltd. of Japan manufactures to use strainer, trade(brand)name " コ Application パ Network ト カ ー ト リ ッ ジ Off ィ ル タ ー MCP-1-C10S "] filter, prepare water-dispersed acrylic class binder composition.
(formation of binder layer, the making of adhesive sheet)
Then, by aforementioned water-dispersed acrylic class binder composition coating (coating) obtained, to PET film, (Toyo Boseki K.K manufactures the applicator using テ ス タ ー Industry Co., Ltd to manufacture, trade(brand)name " E7415 ", thickness: 38 μm) corona treatment face on make dried thickness be 15 μm, then, in heated air circulation type baking oven, 120 DEG C of dryings 2 minutes, then 50 DEG C of maintenances (aging) 3 days, adhesive sheet is obtained.
< embodiment 1-2 ~ 1-8 and comparative example 1-1 ~ 1-6>
As shown in Table 1 and Table 2, the kind, use level etc. of feed change monomer and emulsifying agent etc., prepare monomer emulsion in the same manner as embodiment 1-1.In addition, use described monomer emulsion, obtain water-dispersed acrylic class binder composition and adhesive sheet in the same manner as embodiment 1-1.In addition, the insoluble component content of solvent of the acrylic emulsions type polymkeric substance obtained in each embodiment, comparative example and the weight-average molecular weight (Mw) of solvent-soluble composition are as shown in Table 1 and Table 2.
[evaluation]
For the water-dispersed acrylic class binder composition obtained in embodiment and comparative example and adhesive sheet, evaluated by following measuring method or evaluation method.In addition, evaluation result as shown in Table 1 and Table 2.
(1) elongation at break (making of the acrylic adhesives film after crosslinked) of the acrylic adhesives film after being cross-linked
The water-dispersed acrylic class binder composition obtained in embodiment and comparative example is applied to and utilizes polysiloxane to carry out (the Mitsubishi Plastics Inc's manufacture of surface-treated PET film, " MRF38 ") polysiloxane treated side on make dried thickness be 50 μm, then, 120 DEG C of dryings 2 minutes in heated air circulation type baking oven, carry out maintenance in three days at 50 DEG C, obtain cross linking membrane (the acrylic adhesives film after crosslinked).
(mensuration of elongation at break)
Then, by aforementioned cross linking membrane (the acrylic adhesives film after crosslinked) volume circle, columned sample (long 50mm, sectional area (floorage) 1mm is made 2).
Use tensile testing machine, 23 DEG C, measure under the environment of 50%RH.Setting chuck makes the initial length (initial chuck interval) measured be 10mm, under the condition of draw speed 50mm/ minute, carry out tension test, measures the elongation [elongation at break (breaking point elongation)] of breaking point.
In addition, elongation at break (breaking point elongation) represents elongation when test film (the cylindric sample of cross linking membrane) ruptures in tension test, is calculated by following formula." elongation at break (breaking point elongation) " (%)=(length (during fracture chuck interval) of test film " during the fracture "-" initial length (10mm) ") ÷ (" initial length (10mm) ") × 100
(2) the insoluble component content of solvent of the acrylic adhesives film after being cross-linked
Cross linking membrane (the acrylic adhesives film after crosslinked) is made by the method same with aforementioned (1).
Then, according to aforesaid " measuring method of the insoluble component content of solvent ", the insoluble component content of solvent of aforementioned cross linking membrane is measured.
Get the aforementioned cross linking membrane of about 0.1g (the acrylic adhesives film after crosslinked), by the porous tetrafluoroethylene sheet (trade(brand)name " NTF1122 " of mean pore size 0.2 μm, Nitto Denko Corp manufactures) parcel, then tighten with kite string, measure weight now, using this weight as the front weight of dipping.In addition, before this dipping, weight is the gross weight of cross linking membrane (cross linking membrane got above), tetrafluoroethylene sheet and kite string.In addition, the total weight of tetrafluoroethylene sheet and kite string is measured, using this weight as packing bag weight.
Then, by above-mentioned cross linking membrane tetrafluoroethylene sheet parcel and the object tightened with kite string and obtain (being called " sample ") puts into the 50ml container being full of ethyl acetate, and 23 DEG C leave standstill 7 days.Then, take out sample (after ethyl acetate process) from container, transfer in aluminum cup, 130 DEG C in drying machine dry 2 hours and remove ethyl acetate, then gravimetry, using this weight as weight after dipping.Further, the insoluble component content of solvent is calculated by following formula.
(in above formula, d is weight after dipping, and e is packing bag weight, and f is weight before dipping in the insoluble component content of solvent (% by weight)=(d-e)/(f-e) × 100.)
(3) electrostatic potential is peeled off
The adhesive sheet of making is cut into the size of width 70mm, length 130mm, after partition is peeled off, hand roller is utilized to be crimped onto in advance except being pasted onto acrylic acid resin plate (mitsubishi rayon manufacture after electricity, ア Network リ ラ イ ト, thickness: 1mm, width: 70mm, length: 100mm) on polarizing plate [Nitto Denko Corp manufactures, trade(brand)name " SEG1425DU "] surface, make single end give prominence to 30mm.Then, place after 1 day under the environment of 23 DEG C × 24 ± 2%RH, as shown in Figure 1 sample is set to the position of regulation.The single end of outstanding 30mm is fixed on sutomatic winding machine, peels off with the condition of peel angle 150 °, peeling rate 10m/ minute.The potential measurement device (springtime, Motor Corporation manufactured, KSD-0103) being fixed to prescribed position is utilized to measure the current potential on the polarizing plate surface now produced.The distance of sample and potential measurement device is set as 100mm when measuring acrylic acid resin plate surface.In addition, carry out under being determined at the environment of 23 DEG C × 24 ± 2%RH.
In addition, as the stripping electrostatic potential (absolute value) of adhesive sheet of the present invention, be preferably below 1.0kV, be more preferably below 0.8kV.When described stripping electrostatic potential is more than 1.0kV, when adhesive sheet is peeled off, easily adsorb dust, therefore not preferred.
(4) anti-peeling force (bounding force) ascending (initial peeling force)
The adhesive sheet of making is cut into the size of width 25mm, length 100mm, after partition is peeled off, (テ ス タ ー Industry Co., Ltd manufactures to use labelling machine, small-sized labelling machine), condition lower floor at 0.25MPa, 0.3m/ minute is pressed onto polarizing plate, and (Nitto Denko Corp manufactures, SEG1425DU, width: 70mm, length: 100mm) on, make assess sample.After lamination, place under the environment of 23 DEG C × 50%RH after 30 minutes, use universal tensile testing machine, be determined at peeling rate 10m/ minute, peeling force (bounding force) (N/25mm) when peeling off under the condition of peel angle 180 ° be as " initial peeling force ".Carry out under being determined at the environment of 23 DEG C × 50%RH.
In addition, as the initial peeling force of adhesive sheet of the present invention, be preferably 0.1 ~ 1.5N/25mm, be more preferably 0.2 ~ 1.2N/25mm.By aforementioned peeling force is adjusted to below 1.5N/25mm, in the manufacturing process of polarizing plate or liquid crystal indicator, adhesive sheet is easily peeled off, and productivity, operability improve, therefore preferably.In addition, by aforementioned peeling force is adjusted to more than 0.1N/25mm, tilting or the stripping of adhesive sheet in manufacturing process can be suppressed, give full play to the defencive function as pressure-sensitive adhesive sheet for surface protection, therefore preferably.
(40 DEG C × 1 week paste preserve after peeling force: through time peeling force)
In addition, after the sample aforesaid adhesive sheet and polarizing plate pasted preserves 1 week under the environment of 40 DEG C, 23 DEG C, place 2 hours under the environment of 50%RH, then under the condition of peeling rate 10m/ minute, carry out 180 ° of stripping tests, measure adhesive sheet to peeling force (bounding force) (N/25mm) of polarizing plate as " through time peeling force ".
In addition, initial peeling force with through time peeling force difference [(through time peeling force)-(initial peeling force)] if be less than 0.5N/25mm, then can judge that anti-peeling force (bounding force) is ascending excellent.In addition, the initial peeling force of adhesive sheet of the present invention with through time peeling force difference [(through time peeling force)-(initial peeling force)] be preferably less than 0.5N/25mm, be more preferably 0.0 ~ 0.2N/25mm.When aforementioned difference is more than 0.5N/25mm, anti-peeling force (bounding force) ascending difference sometimes, the overburden operation again of adhesive sheet declines.
(5) contaminative (albefaction) [adding wet test]
(テ ス タ ー Industry Co., Ltd manufactures the adhesive sheet obtained in embodiment and comparative example (sample size: wide 25mm × long 100mm) to be used labelling machine, small-sized labelling machine), under the condition of 0.25MPa, 0.3m/ minute, pasting polarizing plate, (Nitto Denko Corp manufactures, trade(brand)name " SEG1425DU ", size: wide 70mm × long 120mm) on.
After the polarizing plate being pasted with aforementioned adhesion sheet is placed 4 hours at 80 DEG C under the state being pasted with adhesive sheet, adhesive sheet is peeled off.Then, by the polarizing plate after release adhesive sheet, under humidified ambient, (23 DEG C, 90%RH) places 12 hours, and visual observation polarizing plate surface, with following benchmark evaluation low stain.After adhesive sheet is pasted/peeled off, under humidified condition (high humidity), as when the polarizing plate of adherend produces albefaction, as the surface protective film purposes of optical component, low stain is insufficient.
Low stain good (zero): do not observe change in the part being pasted with adhesive sheet and the part of not pasting adhesive sheet
Low stain slightly poor (△): slightly observe albefaction in the part being pasted with adhesive sheet.
Low stain difference (×): clearly observe albefaction in the part being pasted with adhesive sheet.
(6) outward appearance (with or without depression)
The state of the adhesive layer surface of the adhesive sheet obtained in visual observation embodiment and comparative example.Be determined at the number of the defect (depression) in the range of observation of vertical 10cm × horizontal 10cm, and with following benchmark evaluation.
Defect number 0 ~ 100: outward appearance good (zero)
Defect number more than 101: appearance poor (×)
Table 1
Table 2
In table 1 and table 2, use level, the addition of polymerization starter, emulsifying agent, crosslinking catalyst represent with actual use level (use levels of commodity).In addition, acrylic emulsions type polymkeric substance represents with the weight of solids component.
In addition, about the cooperation content in table 1, represent the weight of solids component.In addition, the breviary symbol used in table 1 is as described below.
2EHA:2-ethylhexyl acrylate (2-EHA)
MMA: methylmethacylate (methyl methacrylate)
Vac: vinyl-acetic ester
DEAA: acrylamide
AA: vinylformic acid
HS10: Di-ichi Kogyo Seiyaku Co., Ltd. manufactures, trade(brand)name " ア Network ア ロ Application HS-10 " (reactive non-ionic anion type emulsifying agent)
SE-10N: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ リ ア ソ ー プ SE-10N " (reactive non-ionic anion type emulsifying agent)
T/C (テ ト ラ ッ De C): Mitsubishi Gas Chemical Co., Ltd manufactures, trade(brand)name " TETRAD-C " (two (N, the N-diglycidyl amino methyl) hexanaphthene of 1,3-), epoxy equivalent (weight): 110, functional group number: 4)
T/X (テ ト ラ ッ De X): Mitsubishi Gas Chemical Co., Ltd manufactures, trade(brand)name " TETRAD-X " (two (N, the N-diglycidyl amino methyl) benzene of 1,3-), epoxy equivalent (weight): 100, functional group number: 4)
CC-36: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ コ ー Le CC-36 " (polyether-type aliquat)
CIL-313: Japanese カ ー リ ッ ト Co., Ltd. manufactures, N-butyl-3-picoline fluoroform sulphonate (water-soluble)
EtMePy-EF21: Mitsubishi マ テ リ ア Le electronization becomes Co., Ltd. to manufacture, N-ethyl-3-picoline perfluor esilate (water-soluble)
EMI-EF31: Mitsubishi マ テ リ ア Le electronization becomes Co., Ltd. to manufacture, N-ethyl-3-methylimidazole perfluor propanesulfonic acid salt (water-soluble)
IL-130: Di-ichi Kogyo Seiyaku Co., Ltd. manufactures, 1-methyl isophthalic acid-propylpiperdine two (fluorine sulphonyl) imines (water-insoluble)
25R-1: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ プ Le ロ ニ ッ Network 25R-1 " (PO containing ratio: 90 % by weight, number-average molecular weight 2800, polyether type defoamer)
17R-4: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ プ Le ロ ニ ッ Network 17R-4 " (PO containing ratio: 60 % by weight, number-average molecular weight 2500, polyether type defoamer)
Can be confirmed by the result of table 1, in an embodiment, obtain static electricity resistance, adhesion characteristic, anti-through time peeling force (bounding force) ascending excellent, and appearance characteristics and the excellent adhesive sheet of low stain.
On the other hand, as can be seen from the result of table 2, in comparative example 1-1, do not coordinate specific monomer (methyl methacrylate etc.) and water-soluble (wetting ability) ionic liquid, therefore obtain the result of static electricity resistance, appearance characteristics difference.In addition, in comparative example 1-2, do not coordinate specific monomer (methyl methacrylate etc.), and coordinated hydrophobic ionic liquid, therefore obtain the result of contaminative, appearance characteristics difference.In comparative example 1-3, do not coordinate specific monomer (methyl methacrylate etc.) and water-soluble (wetting ability) ionic liquid, and coordinate the quaternary ammonium salt as crosslinking catalyst, therefore obtain the result of static electricity resistance, contaminative, appearance characteristics difference.Particularly, owing to having coordinated aforementioned crosslinking catalyst, the result of contaminative difference has therefore been obtained.In comparative example 1-4, non-hydrous water dissolubility (wetting ability) ionic liquid, therefore obtains the result of static electricity resistance difference.In addition, the weight-average molecular weight of the solvent-soluble composition of acrylic emulsions type multipolymer is high, therefore obtains the result that contaminative is slightly poor.In addition, in comparative example 1-5, do not coordinate specific monomer (methyl methacrylate etc.), therefore obtain the result of appearance characteristics difference.In comparative example 1-6, do not coordinate specific monomer (methyl methacrylate etc.), and the use level of (methyl) alkyl acrylate monomer exceedes required scope, therefore obtain that adhesion characteristic, anti-peeling force are ascending, the result of appearance characteristics, contaminative difference.In addition, non-hydrous water dissolubility (wetting ability) ionic liquid, therefore obtains the result that static electricity resistance is also poor.
< the 2nd invention group >
< embodiment 2-1>
(preparation of acrylic emulsions type polymkeric substance)
(Di-ichi Kogyo Seiyaku Co., Ltd. manufactures for hydrous water 90 weight part and 2-EHA as shown in table 3 (2EHA) 94 weight part, methyl methacrylate (MMA) 2 weight part, vinylformic acid (AA) 4 weight part, reactive non-ionic anion type emulsifying agent in a reservoir, trade(brand)name " ア Network ア ロ Application HS-10 ") 6 weight parts, then be uniformly mixed with super mixer, prepare monomer emulsion.Then, in the reaction vessel with prolong, nitrogen introducing tube, thermometer and agitator, add in the monomer emulsion of water 50 weight part, polymerization starter (ammonium persulphate) 0.01 weight part and above-mentioned preparation the amount being equivalent to 10 % by weight, while stirring, carry out letex polymerization in 1 hour at 75 DEG C.Then, then add polymerization starter (ammonium persulphate) 0.07 weight part, then while stirring, added remaining whole monomer emulsion (being equivalent to the amount of 90 % by weight) with 3 hours, then 75 DEG C of reactions 3 hours.Then, be cooled to 30 DEG C, the ammoniacal liquor adding concentration 10 % by weight is adjusted to pH8, the aqueous dispersions of preparation acrylic emulsions type polymkeric substance.
(preparation of water-dispersed acrylic class binder composition)
In the aqueous dispersions of the aforementioned acrylic emulsions type polymkeric substance obtained, relative to acrylic emulsions type polymkeric substance (solids component) 100 weight part, use agitator 23 DEG C, 300rpm, be uniformly mixed ionic liquid [IL-110 that Di-ichi Kogyo Seiyaku Co., Ltd. manufactures, 1-ethyl-3-methylimidazole under the agitation condition of 10 minutes two (fluorine sulphonyl) imines (water-insoluble ionic liquid)] 0.5 weight part, as water-insoluble linking agent epoxies linking agent [Mitsubishi Gas Chemical Co., Ltd manufacture, trade(brand)name " TETRAD-C ", 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, epoxy equivalent (weight): 110, functional group number: 4] 3 weight parts, prepare water-dispersed acrylic class binder composition.
(formation of binder layer, the making of adhesive sheet)
Then, by aforementioned water-dispersed acrylic class binder composition coating (coating) obtained, to PET film, (Toyo Boseki K.K manufactures the applicator using テ ス タ ー Industry Co., Ltd to manufacture, trade(brand)name " E7415 ", thickness: 38 μm) corona treatment face on make dried thickness be 15 μm, then, in heated air circulation type baking oven, 120 DEG C of dryings 2 minutes, then 50 DEG C of maintenances (aging) 3 days, adhesive sheet is obtained.
< embodiment 2-2 ~ 2-8, comparative example 2-1 ~ 2-5>
As shown in Table 3 and Table 4, the kind, use level etc. of feed change monomer and emulsifying agent etc., prepare monomer emulsion in the same manner as embodiment 2-1.In addition, use described monomer emulsion, obtain water-dispersed acrylic class binder composition and adhesive sheet in the same manner as embodiment 2-1.In addition, the insoluble component content of solvent of the acrylic emulsions type polymkeric substance obtained in each embodiment, comparative example and the weight-average molecular weight (Mw) of solvent-soluble composition are as shown in Table 3 and Table 4.
[evaluation]
For the water-dispersed acrylic class binder composition obtained in embodiment and comparative example and adhesive sheet, evaluated by following measuring method or evaluation method.In addition, evaluation result as shown in Table 3 and Table 4.
(1) elongation at break (making of the acrylic adhesives film after crosslinked) of the acrylic adhesives film after being cross-linked
The water-dispersed acrylic class binder composition obtained in embodiment and comparative example is applied to and utilizes polysiloxane to carry out (the Mitsubishi Plastics Inc's manufacture of surface-treated PET film, " MRF38 ") polysiloxane treated side on make dried thickness be 50 μm, then, 120 DEG C of dryings 2 minutes in heated air circulation type baking oven, carry out maintenance in three days at 50 DEG C, obtain cross linking membrane (the acrylic adhesives film after crosslinked).
(mensuration of elongation at break)
Then, by aforementioned cross linking membrane (the acrylic adhesives film after crosslinked) volume circle, columned sample (long 50mm, sectional area (floorage) 1mm is made 2).
Use tensile testing machine, 23 DEG C, measure under the environment of 50%RH.Setting chuck makes the initial length (initial chuck interval) measured be 10mm, under the condition of draw speed 50mm/ minute, carry out tension test, measures the elongation [elongation at break (breaking point elongation)] of breaking point.
In addition, elongation at break (breaking point elongation) represents elongation when test film (the cylindric sample of cross linking membrane) ruptures in tension test, is calculated by following formula." elongation at break (breaking point elongation) " (%)=(length (during fracture chuck interval) of test film " during the fracture "-" initial length (10mm) ") ÷ (" initial length (10mm) ") × 100
(2) the insoluble component content of solvent of the acrylic adhesives film after being cross-linked
Cross linking membrane (the acrylic adhesives film after crosslinked) is made by the method same with aforementioned (1).
Then, according to aforesaid " measuring method of the insoluble component content of solvent ", the insoluble component content of solvent of aforementioned cross linking membrane is measured.
Get the aforementioned cross linking membrane of about 0.1g (the acrylic adhesives film after crosslinked), by the porous tetrafluoroethylene sheet (trade(brand)name " NTF1122 " of mean pore size 0.2 μm, Nitto Denko Corp manufactures) parcel, then tighten with kite string, measure weight now, using this weight as the front weight of dipping.In addition, before this dipping, weight is the gross weight of cross linking membrane (cross linking membrane got above), tetrafluoroethylene sheet and kite string.In addition, the total weight of tetrafluoroethylene sheet and kite string is measured, using this weight as packing bag weight.
Then, by above-mentioned cross linking membrane tetrafluoroethylene sheet parcel and the object tightened with kite string and obtain (being called " sample ") puts into the 50ml container being full of ethyl acetate, and 23 DEG C leave standstill 7 days.Then, take out sample (after ethyl acetate process) from container, transfer in aluminum cup, 130 DEG C in drying machine dry 2 hours and remove ethyl acetate, then gravimetry, using this weight as weight after dipping.Further, the insoluble component content of solvent is calculated by following formula.
(in above formula, d is weight after dipping, and e is packing bag weight, and f is weight before dipping in the insoluble component content of solvent (% by weight)=(d-e)/(f-e) × 100.)
(3) electrostatic potential is peeled off
The adhesive sheet of making is cut into the size of width 70mm, length 130mm, after partition is peeled off, hand roller is utilized to be crimped onto in advance except being pasted onto acrylic acid resin plate (mitsubishi rayon manufacture after electricity, ア Network リ ラ イ ト, thickness: 1mm, width: 70mm, length: 100mm) on polarizing plate [Nitto Denko Corp manufactures, trade(brand)name " SEG1425DU "] surface, make single end give prominence to 30mm.Then, place after 1 day under the environment of 23 DEG C × 24 ± 2%RH, as shown in Figure 1 sample is set to the position of regulation.The single end of outstanding 30mm is fixed on sutomatic winding machine, peels off with the condition of peel angle 150 °, peeling rate 10m/ minute.The potential measurement device (springtime, Motor Corporation manufactured, KSD-0103) being fixed to prescribed position is utilized to measure the current potential on the polarizing plate surface now produced.The distance of sample and potential measurement device is set as 100mm when measuring acrylic acid resin plate surface.In addition, carry out under being determined at the environment of 23 DEG C × 24 ± 2%RH.
In addition, as the stripping electrostatic potential (absolute value) of adhesive sheet of the present invention, be preferably below 1.0kV, be more preferably below 0.8kV.When described stripping electrostatic potential is more than 1.0kV, when adhesive sheet is peeled off, easily adsorb dust, therefore not preferred.
(4) anti-peeling force (bounding force) ascending (initial peeling force)
The adhesive sheet of making is cut into the size of width 25mm, length 100mm, after partition is peeled off, (テ ス タ ー Industry Co., Ltd manufactures to use labelling machine, small-sized labelling machine), condition lower floor at 0.25MPa, 0.3m/ minute is pressed onto polarizing plate, and (Nitto Denko Corp manufactures, SEG1425DU, width: 70mm, length: 100mm) on, make assess sample.After lamination, place under the environment of 23 DEG C × 50%RH after 30 minutes, use universal tensile testing machine, be determined at peeling rate 10m/ minute, peeling force (bounding force) (N/25mm) when peeling off under the condition of peel angle 180 ° be as " initial peeling force ".Carry out under being determined at the environment of 23 DEG C × 50%RH.
In addition, as the initial peeling force of adhesive sheet of the present invention, be preferably 0.1 ~ 1.5N/25mm, be more preferably 0.2 ~ 1.2N/25mm.By aforementioned peeling force is adjusted to below 1.5N/25mm, in the manufacturing process of polarizing plate or liquid crystal indicator, adhesive sheet is easily peeled off, and productivity, operability improve, therefore preferably.In addition, by aforementioned peeling force is adjusted to more than 0.1N/25mm, tilting or the stripping of adhesive sheet in manufacturing process can be suppressed, give full play to the defencive function as pressure-sensitive adhesive sheet for surface protection, therefore preferably.
(40 DEG C × 1 week paste preserve after peeling force: through time peeling force)
In addition, after the sample aforesaid adhesive sheet and polarizing plate pasted preserves 1 week under the environment of 40 DEG C, 23 DEG C, place 2 hours under the environment of 50%RH, then under the condition of peeling rate 10m/ minute, carry out 180 ° of stripping tests, measure adhesive sheet to peeling force (bounding force) (N/25mm) of polarizing plate as " through time peeling force ".
In addition, initial peeling force with through time peeling force difference [(through time peeling force)-(initial peeling force)] if be less than 0.5N/25mm, then can judge that anti-peeling force (bounding force) is ascending excellent.In addition, the initial peeling force of adhesive sheet of the present invention with through time peeling force difference [(through time peeling force)-(initial peeling force)] be preferably less than 0.5N/25mm, be more preferably 0.0 ~ 0.2N/25mm.When aforementioned difference is more than 0.5N/25mm, anti-peeling force (bounding force) ascending difference sometimes, the overburden operation again of adhesive sheet declines.
(5) contaminative (albefaction) [adding wet test]
(テ ス タ ー Industry Co., Ltd manufactures the adhesive sheet obtained in embodiment and comparative example (sample size: wide 25mm × long 100mm) to be used labelling machine, small-sized labelling machine), under the condition of 0.25MPa, 0.3m/ minute, pasting polarizing plate, (Nitto Denko Corp manufactures, trade(brand)name " SEG1425DU ", size: wide 70mm × long 120mm) on.
After the polarizing plate being pasted with aforementioned adhesion sheet is placed 4 hours at 80 DEG C under the state being pasted with adhesive sheet, adhesive sheet is peeled off.Then, by the polarizing plate after release adhesive sheet, under humidified ambient, (23 DEG C, 90%RH) places 12 hours, and visual observation polarizing plate surface, with following benchmark evaluation low stain.After adhesive sheet is pasted/peeled off, under humidified condition (high humidity), as when the polarizing plate of adherend produces albefaction, as the surface protective film purposes of optical component, low stain is insufficient.
Low stain good (zero): do not observe change in the part being pasted with adhesive sheet and the part of not pasting adhesive sheet
Low stain slightly poor (△): slightly observe albefaction in the part being pasted with adhesive sheet.
Low stain difference (×): clearly observe albefaction in the part being pasted with adhesive sheet.
(6) outward appearance (with or without depression, jello)
The state of the adhesive layer surface of the adhesive sheet obtained in visual observation embodiment and comparative example.Be determined at the number of the defect (depression and jello) in the range of observation of vertical 10cm × horizontal 10cm, and with following benchmark evaluation.
Defect number 0 ~ 100: outward appearance good (zero)
Defect number more than 101: appearance poor (×)
Table 3
Table 4
In table 3 and table 4, use level, the addition of polymerization starter, emulsifying agent, crosslinking catalyst represent with actual use level (use levels of commodity).In addition, acrylic emulsions type polymkeric substance represents with the weight of solids component.
In addition, about the cooperation content in table 3, represent the weight of solids component.In addition, the breviary symbol used in table 3 is as described below.
2EHA:2-ethylhexyl acrylate (2-EHA)
MMA: methylmethacylate (methyl methacrylate)
Vac: vinyl-acetic ester
DEAA: acrylamide
AA: vinylformic acid
HS10: Di-ichi Kogyo Seiyaku Co., Ltd. manufactures, trade(brand)name " ア Network ア ロ Application HS-10 " (reactive non-ionic anion type emulsifying agent)
SE-10N: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ リ ア ソ ー プ SE-10N " (reactive non-ionic anion type emulsifying agent)
T/C (テ ト ラ ッ De C): Mitsubishi Gas Chemical Co., Ltd manufactures, trade(brand)name " TETRAD-C " (two (N of 1,3-, N-diglycidyl amino methyl) hexanaphthene), epoxy equivalent (weight): 110, functional group number: 4, water-insoluble linking agent)
T/X (テ ト ラ ッ De X): Mitsubishi Gas Chemical Co., Ltd manufactures, trade(brand)name " TETRAD-X " (two (N of 1,3-, N-diglycidyl amino methyl) benzene), epoxy equivalent (weight): 100, functional group number: 4, water-insoluble linking agent)
CC-36: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ コ ー Le CC-36 " (polyether-type aliquat, crosslinking catalyst)
IL-110: Di-ichi Kogyo Seiyaku Co., Ltd. manufactures, 1-ethyl-3-methylimidazole two (fluorine sulphonyl) imines (water-insoluble ionic liquid)
IL-120: Di-ichi Kogyo Seiyaku Co., Ltd. manufactures, 1-methyl isophthalic acid-propyl pyrrole alkane two (fluorine sulphonyl) imines (water-insoluble ionic liquid)
IL-130: Di-ichi Kogyo Seiyaku Co., Ltd. manufactures, 1-methyl isophthalic acid-propylpiperdine two (fluorine sulphonyl) imines (water-insoluble ionic liquid)
25R-1: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ プ Le ロ ニ ッ Network 25R-1 " (PO containing ratio: 90 % by weight, number-average molecular weight 2800, polyether type defoamer)
17R-4: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ プ Le ロ ニ ッ Network 17R-4 " (PO containing ratio: 60 % by weight, number-average molecular weight 2500, polyether type defoamer)
Can be confirmed by the result of table 3, in an embodiment, obtain static electricity resistance, adhesion characteristic, anti-through time peeling force (bounding force) ascending excellent, and appearance characteristics and the excellent adhesive sheet of low stain.
On the other hand, as can be seen from the result of table 4, in comparative example 2-1, do not coordinate specific monomer and water-insoluble ionic liquid, therefore obtain the result of static electricity resistance, appearance characteristics difference.In addition, in comparative example 2-2, do not coordinate specific monomer, therefore obtain the result of contaminative, appearance characteristics difference.In comparative example 2-3, do not coordinate water-insoluble ionic liquid, therefore obtain the result of static electricity resistance difference.In addition, owing to having coordinated the quaternary ammonium salt as crosslinking catalyst, the result of contaminative difference has therefore been obtained.In comparative example 2-4, do not coordinate water-insoluble ionic liquid, therefore obtain the result of static electricity resistance difference.In addition, in comparative example 2-5, do not coordinate water-insoluble ionic liquid and specific monomer with specific ratio, therefore obtain that not only static electricity resistance but also adhesion characteristic, anti-peeling force are ascending, the result of appearance characteristics, contaminative difference.
< the 3rd invention group >
< embodiment 3-1>
(preparation of acrylic emulsions type polymkeric substance)
(Di-ichi Kogyo Seiyaku Co., Ltd. manufactures for hydrous water 90 weight part and 2-EHA as shown in table 5 (2EHA) 92 weight part, methyl methacrylate (MMA) 4 weight part, vinylformic acid (AA) 4 weight part, reactive non-ionic anion type emulsifying agent in a reservoir, trade(brand)name " ア Network ア ロ Application HS-10 ") 3 weight parts, then be uniformly mixed with super mixer, prepare monomer emulsion.
Then, in the reaction vessel with prolong, nitrogen introducing tube, thermometer and agitator, add in water 50 weight part, polymerization starter (ammonium persulphate) 0.01 weight part and described monomer emulsion the amount being equivalent to 10 % by weight, while stirring, carry out letex polymerization in 1 hour at 65 DEG C.Then, then add polymerization starter (ammonium persulphate) 0.05 weight part, then while stirring, added remaining whole monomer emulsion (being equivalent to the amount of 90 % by weight) with 3 hours, then 75 DEG C of reactions 3 hours.Then, be cooled to 30 DEG C, the ammoniacal liquor adding concentration 10 % by weight is adjusted to pH8, the aqueous dispersions (concentration of acrylic emulsions type polymkeric substance: 41 % by weight) of preparation acrylic emulsions type polymkeric substance.
(preparation of water-dispersed acrylic class binder composition)
In the aqueous dispersions of the aforementioned acrylic emulsions type polymkeric substance obtained, relative to acrylic emulsions type polymkeric substance (solids component) 100 weight part, use agitator at 23 DEG C, 300rpm, epoxies linking agent [the Mitsubishi Gas Chemical Co., Ltd's manufacture as water-insoluble linking agent is uniformly mixed under the agitation condition of 10 minutes, trade(brand)name " TETRAD-C ", 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, epoxy equivalent (weight): 110, functional group number: 4] 2 weight parts, trifluoromethanesulfonic acid lithium [effective constituent 100 % by weight] 1 weight part, prepare water-dispersed acrylic class binder composition.
(formation of binder layer, the making of adhesive sheet)
Then, by aforementioned water-dispersed acrylic class binder composition coating (coating), to PET film, (Toyo Boseki K.K manufactures the applicator using テ ス タ ー Industry Co., Ltd to manufacture, trade(brand)name " E7415 ", thickness: 38 μm) corona treatment face on make dried thickness be 15 μm, then, in heated air circulation type baking oven, 120 DEG C of dryings 2 minutes, then room temperature maintenance (aging) 1 week, adhesive sheet is obtained.
< embodiment 3-2 ~ 3-8, comparative example 3-1 ~ 3-4>
As shown in table 5, the kind, use level etc. of feed change monomer and emulsifying agent etc., prepare monomer emulsion in the same manner as embodiment 3-1.In addition, about the additive do not recorded in table, prepare with the use level same with embodiment 3-1.In addition, use described monomer emulsion, obtain water-dispersed acrylic class binder composition and adhesive sheet in the same manner as embodiment 3-1.
[evaluation]
For the water-dispersed acrylic class binder composition obtained in embodiment and comparative example and adhesive sheet, evaluated by following measuring method or evaluation method.In addition, about evaluation result, as shown in table 5.
The making > of the acrylic adhesives film after < is cross-linked
The water-dispersed acrylic class binder composition obtained in embodiment and comparative example is applied to and utilizes polysiloxane to carry out (the Mitsubishi Plastics Inc's manufacture of surface-treated PET film, " MRF38 ") polysiloxane treated side on make dried thickness be 50 μm, then, 120 DEG C of dryings 2 minutes in heated air circulation type baking oven, carry out maintenance in three days at 50 DEG C, obtain cross linking membrane (the acrylic adhesives film after crosslinked).
The mensuration > of < elongation at break
Then, by aforementioned cross linking membrane (the acrylic adhesives film after crosslinked) volume circle, columned sample (long 50mm, sectional area (floorage) 1mm is made 2).
Use tensile testing machine, 23 DEG C, measure under the environment of 50%RH.Setting chuck makes the initial length (initial chuck interval) measured be 10mm, under the condition of draw speed 50mm/ minute, carry out tension test, measures the elongation [elongation at break (breaking point elongation)] of breaking point.
In addition, elongation at break (breaking point elongation) represents elongation when test film (the cylindric sample of cross linking membrane) ruptures in tension test, is calculated by following formula.
" elongation at break (breaking point elongation) " (%)=100 × (length (during fracture chuck interval) of test film " during the fracture "-" initial length (10mm) ")/(" initial length (10mm) ")
The insoluble component content > of solvent of the acrylic adhesives film after < is cross-linked
Made by the method same with aforementioned cross linking membrane (the acrylic adhesives film after crosslinked).Then, according to aforesaid " measuring method of the insoluble component content of solvent ", the insoluble component content of solvent of aforementioned cross linking membrane is measured.
Get the aforementioned cross linking membrane of about 0.1g (the acrylic adhesives film after crosslinked), by the porous tetrafluoroethylene sheet (trade(brand)name " NTF1122 " of mean pore size 0.2 μm, Nitto Denko Corp manufactures) parcel, then tighten with kite string, measure weight now, using this weight as the front weight of dipping.In addition, before this dipping, weight is the gross weight of cross linking membrane (cross linking membrane got above), tetrafluoroethylene sheet and kite string.In addition, the total weight of tetrafluoroethylene sheet and kite string is measured, using this weight as packing bag weight.
Then, by above-mentioned cross linking membrane tetrafluoroethylene sheet parcel and the object tightened with kite string and obtain (being called " sample ") puts into the 50ml container being full of ethyl acetate, and 23 DEG C leave standstill 7 days.Then, take out sample (after ethyl acetate process) from container, transfer in aluminum cup, 130 DEG C in drying machine dry 2 hours and remove ethyl acetate, then gravimetry, using this weight as weight after dipping.Further, the insoluble component content of solvent is calculated by following formula.
(in above formula, d is weight after dipping, and e is packing bag weight, and f is weight before dipping in the insoluble component content of solvent (% by weight)=(d-e)/(f-e) × 100.)
< peels off electrostatic potential >
The adhesive sheet of making is cut into the size of width 70mm, length 130mm, after partition is peeled off, hand roller is utilized to be crimped onto in advance except being pasted onto acrylic acid resin plate (mitsubishi rayon manufacture after electricity, ア Network リ ラ イ ト, thickness: 1mm, width: 70mm, length: 100mm) on polarizing plate [Nitto Denko Corp manufactures, trade(brand)name " SEG1425DU "] surface, make single end give prominence to 30mm.Then, place after 1 day under the environment of 23 DEG C × 24 ± 2%RH, as shown in Figure 1 sample is set to the position of regulation.The single end of outstanding 30mm is fixed on sutomatic winding machine, peels off with the condition of peel angle 150 °, peeling rate 10m/ minute.The potential measurement device (springtime, Motor Corporation manufactured, KSD-0103) being fixed to prescribed position is utilized to measure the current potential on the polarizing plate surface now produced.The distance of sample and potential measurement device is set as 100mm when measuring acrylic acid resin plate surface.In addition, carry out under being determined at the environment of 23 DEG C × 24 ± 2%RH.
In addition, as the stripping electrostatic potential (absolute value) of adhesive sheet of the present invention, be preferably below 1.0kV, be more preferably below 0.8kV.When described stripping electrostatic potential is more than 1.0kV, the liquid crystal aligning as the polarizing plate of adherend is disorderly, therefore not preferred.
< initial adhesion (stripping) power >
The adhesive sheet of making is cut into the size of width 25mm, length 100mm, after partition is peeled off, (テ ス タ ー Industry Co., Ltd manufactures to use labelling machine, small-sized labelling machine), condition lower floor at 0.25MPa, 0.3m/ minute is pressed onto polarizing plate, and (Nitto Denko Corp manufactures, SEG1425DU, width: 70mm, length: 100mm) on, make assess sample.
After lamination, place after 30 minutes under the environment of 23 DEG C × 50%RH, use universal tensile testing machine, be determined at peeling rate 0.3m/ minute, bounding force (N/25mm) when peeling off under the condition of peel angle 180 ° is as " Initial adhesion ".Carry out under being determined at the environment of 23 DEG C × 50%RH.
In addition, as the Initial adhesion of adhesive sheet of the present invention, be preferably 0.01 ~ 0.5N/25mm, be more preferably 0.02 ~ 0.3N/25mm.By aforementioned peeling force is adjusted to below 0.5N/25mm, in the manufacturing process of polarizing plate or liquid crystal indicator, adhesive sheet is easily peeled off, and productivity, operability improve, therefore preferably.In addition, by aforementioned adhesion power is adjusted to more than 0.01N/25mm, tilting or the stripping of adhesive sheet in manufacturing process can be suppressed, give full play to the defencive function as pressure-sensitive adhesive sheet for surface protection, therefore preferably.
< contaminative (albefaction) [adding wet test] >
(テ ス タ ー Industry Co., Ltd manufactures the adhesive sheet obtained in embodiment and comparative example (sample size: wide 25mm × long 100mm) to be used labelling machine, small-sized labelling machine), under the condition of 0.25MPa, 0.3m/ minute, pasting polarizing plate, (Nitto Denko Corp manufactures, trade(brand)name " SEG1425DU ", size: wide 70mm × long 120mm) on.
After the polarizing plate being pasted with aforementioned adhesion sheet is placed 4 hours at 80 DEG C under the state being pasted with adhesive sheet, adhesive sheet is peeled off.Then, by the polarizing plate after release adhesive sheet, under humidified ambient, (23 DEG C, 90%RH) places 12 hours, and visual observation polarizing plate surface, with following benchmark evaluation low stain.After adhesive sheet is pasted/peeled off, under humidified ambient (high humidity), as when the polarizing plate of adherend produces albefaction, as the surface protective film purposes of optical component, low stain is insufficient.
Low stain good (zero): do not observe change in the part being pasted with adhesive sheet and the part of not pasting adhesive sheet
Low stain difference (×): be pasted with the partially observable albefaction of adhesive sheet
< appearance characteristics (with or without depression, jello) >
The state of the adhesive layer surface of the adhesive sheet obtained in visual observation embodiment and comparative example.Be determined at the number of the defect (depression and jello) in the range of observation of vertical 10cm × horizontal 10cm, and with following benchmark evaluation.
Defect number 0 ~ 100: outward appearance good (zero)
Defect number more than 101: appearance poor (×)
Table 5
In addition, about the cooperation content in table 5, represent the weight of solids component.In addition, the breviary symbol used in table 5 is as described below.
2EHA: 2-EHA (2-ethylhexyl acrylate)
MMA: methyl methacrylate (methylmethacrylic acid)
Vac: vinyl-acetic ester
DEAA: acrylamide
AA: vinylformic acid
HS10: Di-ichi Kogyo Seiyaku Co., Ltd. manufactures, trade(brand)name " ア Network ア ロ Application HS-10 " (reactive non-ionic anion type emulsifying agent)
SE-10N: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ リ ア ソ ー プ SE-10N " (reactive non-ionic anion type emulsifying agent)
T/C (テ ト ラ ッ De C): Mitsubishi Gas Chemical Co., Ltd manufactures, trade(brand)name " TETRAD-C " (1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene), epoxy equivalent (weight): 110, functional group number: 4) (water-insoluble linking agent)
T/X (テ ト ラ ッ De X): Mitsubishi Gas Chemical Co., Ltd manufactures, trade(brand)name " TETRAD-X " (two (N, the N-diglycidyl amino methyl) benzene of 1,3-), epoxy equivalent (weight): 100, functional group number: 4) (water-insoluble linking agent)
LiCF 3sO 3: trifluoromethanesulfonic acid lithium (effective constituent 50 % by weight), fluorine-containing an alkali metal salt (antistatic agent)
SF-106:ADEKA manufactures, trade(brand)name " ア デ カ ミ Application SF-106 " (dimethyl dialkyl oxygen ethylidene ammonium chloride, solids component 80 % by weight, non-alkali metal salt) (antistatic agent)
17R-2: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ プ Le ロ ニ ッ Network 17R-2 " (number-average molecular weight 2000, PO containing ratio: 80 % by weight) (polyether type defoamer)
17R-4: Asahi Denka Co., Ltd. manufactures, trade(brand)name " ア デ カ プ Le ロ ニ ッ Network 17R-4 " (number-average molecular weight 2500, PO containing ratio: 60 % by weight) (polyether type defoamer)
KF-353: organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI manufactures, and trade(brand)name " KF-353 " (containing inferior ethoxyl polysiloxane, HLB value: 10)
Can be confirmed by the evaluation result of table 5, in whole embodiment, obtain the excellent binder layer of static electricity resistance, adhesion characteristic, low stain and appearance characteristics (adhesive sheet), be suitable for optical applications etc.
On the other hand, in comparative example 3-1, do not coordinate monomer (iii) and an alkali metal salt as antistatic agent, therefore obtain the result of appearance characteristics and static electricity resistance difference.In addition, in comparative example 3-2, do not coordinate monomer (iii), but coordinated the antistatic agent beyond an alkali metal salt, therefore can not realize low stain, and result does not obtain appearance characteristics and static electricity resistance.In comparative example 3-3, the mixing ratio of (methyl) alkyl acrylate (i) as main component is set as lower than required scope, and improve the mixing ratio of other starting monomer, in comparative example 3-4, do not coordinate containing carboxyl unsaturated monomer (ii), therefore, when preparing acrylic emulsions type polymkeric substance, producing condensation product, can not adhesive sheet be made.
Reference numeral
1 potential measurement device
2 adhesive sheets
3 polarizing plates
4 acrylic acid resin plates
5 sample stationary platens

Claims (23)

1. a water-dispersed acrylic class binder composition, it is characterized in that, containing the acrylic emulsions type polymkeric substance formed as monomer component using at least one monomer (iii) in alkyl methacrylate (i), the group that is made up of methyl methacrylate, vinyl-acetic ester and acrylamide containing carboxyl unsaturated monomer (ii) and being selected from and ionic compound
Containing the described alkyl methacrylate (i) of 70 ~ 99.5 % by weight in the total amount of described monomer component,
Described acrylic emulsions type polymkeric substance obtains by using the reactive emulsifier containing free redical polymerization functional group in molecule to carry out being polymerized.
2. water-dispersed acrylic class binder composition as claimed in claim 1, it is characterized in that, described ionic compound is ionic liquid and/or an alkali metal salt.
3. water-dispersed acrylic class binder composition as claimed in claim 1, it is characterized in that, described ionic liquid is water-insoluble ionic liquid and/or water soluble ion liquid.
4. water-dispersed acrylic class binder composition as claimed in claim 1, is characterized in that, containing the described monomer (ii) of 0.5 ~ 10 % by weight in the total amount of monomer component.
5. water-dispersed acrylic class binder composition as claimed in claim 1, is characterized in that, containing the described monomer (iii) of 0.5 ~ 10 % by weight in the total amount of monomer component.
6. water-dispersed acrylic class binder composition as claimed in claim 2, it is characterized in that, described ionic liquid contains at least one positively charged ion in the group being selected from the cation composition represented by following formula (A) ~ (E),
R in formula (A) arepresenting the alkyl of carbonatoms 4 ~ 20, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, R band R cidentical or different, represent the alkyl of hydrogen or carbonatoms 1 ~ 16, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, wherein, when nitrogen-atoms has double bond, there is not R c;
R in formula (B) drepresenting the alkyl of carbonatoms 2 ~ 20, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, R e, R fand R gidentical or different, representing the alkyl of hydrogen or carbonatoms 1 ~ 16, can be the functional group of a part by hybrid atom MCM-41 of described alkyl;
R in formula (C) hrepresenting the alkyl of carbonatoms 2 ~ 20, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, R i, R jand R kidentical or different, representing the alkyl of hydrogen or carbonatoms 1 ~ 16, can be the functional group of a part by hybrid atom MCM-41 of described alkyl;
Z in formula (D) represents nitrogen-atoms, sulphur atom or phosphorus atom, R l, R m, R nand R oidentical or different, represent the alkyl of carbonatoms 1 ~ 20, can be the functional group of a part by hybrid atom MCM-41 of described alkyl, wherein, when Z is sulphur atom, there is not R o;
R in formula (E) prepresenting the alkyl of carbonatoms 1 ~ 18, can be the functional group of a part by hybrid atom MCM-41 of described alkyl.
7. water-dispersed acrylic class binder composition as claimed in claim 2, is characterized in that, the positively charged ion of described ionic liquid is for being selected from by containing imidazoles salt form, containing pyridine salt form, containing morpholine salt form, containing tetramethyleneimine salt form, containing piperidines salt form, ammonium salt-containing type, to contain salt form and at least one contained in the group of sulfonium salt type composition.
8. water-dispersed acrylic class binder composition as claimed in claim 2, it is characterized in that, described ionic liquid contains at least one positively charged ion in the group being selected from the cation composition represented by following formula (a) ~ (d),
R in formula (a) 1represent the alkyl of hydrogen or carbonatoms 1 ~ 3, R 2represent the alkyl of hydrogen or carbonatoms 1 ~ 7,
R in formula (b) 3represent the alkyl of hydrogen or carbonatoms 1 ~ 3, R 4represent the alkyl of hydrogen or carbonatoms 1 ~ 7,
R in formula (c) 5represent the alkyl of hydrogen or carbonatoms 1 ~ 3, R 6represent the alkyl of hydrogen or carbonatoms 1 ~ 7,
R in formula (d) 7represent the alkyl of hydrogen or carbonatoms 1 ~ 3, R 8represent the alkyl of hydrogen or carbonatoms 1 ~ 7.
9. water-dispersed acrylic class binder composition as claimed in claim 2, it is characterized in that, described an alkali metal salt contains fluo anion.
10. water-dispersed acrylic class binder composition as claimed in claim 2, it is characterized in that, described an alkali metal salt is lithium salts.
11. water-dispersed acrylic class binder compositions as claimed in claim 1, is characterized in that, containing oxyalkylene copolymerization.
12. water-dispersed acrylic class binder compositions as claimed in claim 11, is characterized in that, described oxyalkylene copolymerization also contains the polyether type defoamer that following formula (iv) represents,
HO-(PO) n1(EO) m1-H(iv)
In formula (iv), PO represents oxygen propylidene, and EO represents oxygen ethylidene, and m1 represents the integer of 0 ~ 40, and n1 represents the integer of more than 1; The addition form of EO and PO is random or block type.
13. water-dispersed acrylic class binder compositions as claimed in claim 11, is characterized in that, described oxyalkylene copolymerization is the organopolysiloxane that following formula (vi) represents,
In formula, R 1be the organic group of 1 valency, R 2, R 3and R 4for alkylidene group, R 5for hydrogen or organic group, m and n is the integer of 0 ~ 1000, to be 0, a and b when wherein m, n are different be 0 ~ 100 integer, be 0 when wherein a, b are different.
14. water-dispersed acrylic class binder compositions as claimed in claim 1, is characterized in that, also containing have in molecule two or more can with the water-insoluble linking agent of the functional group of carboxyl reaction.
15. water-dispersed acrylic class binder compositions as claimed in claim 1, is characterized in that, for peeling off again.
16. 1 kinds of binder layers, is characterized in that, by the water-dispersed acrylic class binder composition cross-links according to any one of claim 1 ~ 15 being obtained.
17. binder layers as claimed in claim 16, is characterized in that, obtaining by utilizing described water-insoluble cross-linking agents.
18. binder layers as claimed in claim 16, it is characterized in that, the insoluble component content of solvent is more than 90 % by weight, and the elongation at break at 23 DEG C is less than 160%.
19. 1 kinds of adhesive sheets, is characterized in that, are formed with the binder layer according to any one of claim 16 ~ 18 at least one side of supporter.
20. adhesive sheets as claimed in claim 19, it is characterized in that, described supporter is plastic basis material.
21. adhesive sheets as described in claim 19 or 20, is characterized in that, for surface protection.
22. adhesive sheets as claimed in claim 21, is characterized in that, for optical applications.
23. 1 kinds of optical components, is characterized in that, are pasted with adhesive sheet according to claim 22.
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